SUMMER VOCATIONAL TRAINING, 2013

PROJECT REPORT ON -

UREA PRODUCTION AND PROCESS ANALYSIS

SITE: NATIONAL FERTILIZERS LTD., VIJAIPUR.
(FROM 06.06.2013 TO 05.07.2013)

Training Incharge: Mr. M.K. Biswas (Chief manager & HOD- Lab)

Training co-ordinators: Mr. B.N Sharma (Sr. manager-Lab) Mr. D.P. Shrivastava (SR. Manager-Lab)

SUBMITTED BY SAMEER SAXENA 3rdYEAR,

Mr. N.S Hada (Manager-Lab)

IMD INDUSTRIAL CHEMISTRY IIT (BHU), VARANASI.

Acknowledgement
I am thankful to Mr. D.R. Chowdhury (Chief Manager (HRD)) for granting me permission to pursue vocational training in Central laboratory from 06.06.2013 to 05.07.2013. My sincere acknowledgement goes to Mr. M.K. Biswas (Chief Manager, Head of Department-Lab) for allowing me to perform experiments and use the facilities of Central Laboratory during my training tenure. I am also thankful to Mr. B.N. Sharma (Sr. manager-Lab), Mr. O.P. Sharma (Manager-lab), Mr. N.S. Hada (Manager-Lab) and Mr. K.P. Saxena (Sr. Chemist-Lab) who helped a lot in clearing my concepts in the subject and solving my pertinent doubts, without which my training would have never achieved its real meaning. I am also thankful to Mr. R.P. Gupta (A.M. (HRD)) for the kind opportunity he gave me to pursue my summer training in the NFL, Vijaipur plant. Last but not the least I would also like to thank those individual in the Central laboratory that made my vocational training memorable and pleasant.

Sincerely Sameer Saxena 11411EN002 3rdyear, IMD, Industrial Chemistry

2

Indian Institute of Technology (B.H.U), Varanasi.

INDEX Sr. no. Contents

1. 2. About NFL WATER CHEMISTRY OVERVIEW PTP Demineralization Plant CPP AMMONIA PRODUCTION PROCESS

Page No.
4 5 12-16 17-33 34-42 43-52

3.

4.

UREA TECHNOLOGY AND DEVELOPMENT

53-60

5.

VARIOUS EQUIPMENTS AVAILABLE FOR QUALITY CONTROL and LAB TESTING AT CENTRAL LAB, NFL VIJAIPUR VARIOUS WATER QUALITY CONTROL TESTS CARRIED OUT AT CENTRAL LAB, NATIONAL FERTILIZERS LTD. VIJAIPUR EFFLUENT TREATMENT FACILITIES

61-75

5.

76-96

6.

97-101

7.

CONCLUSION

102

National Fertilizers Limited (NFL)

NFL is a schedule A and Mini Ratna Company which was incorporated on 23rd August,1947 for implementation of two fertilizers plants based on gasification technology of Feed stock/ Low Sulphur Heavy Stock at Panipat (Haryana) and Bhatinda(Punjab) having an installed capacity of 5.11 lakh tonnes of urea. In April 1978, the Nangal Group of Plants of fertilizer corporation of India (FCI) was transferred to NFL consequent upon reorganization of NFL-FCI. The Government of India, in 1984, entrusted the company to execute the countrys first inland gas based fertilizers project of 7.26 lakh tonnes Urea capacity in District Guna in Madhya Pradesh. This project was completed well within time & approved coast and received the First prize for Excellence in Project Management `from the Ministry of Programme Implementation, Government of India. The Department of Fertilizers subsequently reassessed the annual installed capacity of Vijaipur plants from 7.26 lakh tonnes of urea to 8.64 lakh tonnes with effect from 1st April, 2000. In order to sustain and enhance the companys growth, NFL successfully completed the revamping of urea plant at Nangal and commercial production commenced from 01.02.2001. The annual installed capacity of Nangal plant thus increased from 3.30 lakh tonnes to 4.78 lakhs tonnes of Urea. Thus, the total annual installed capacity of urea at NFL has reached to 32.31lakh tonnes. NFL Vijaipur unit is very advance and well computerised and called as jewel of crowns of NFL. Vijaipur produces: Kisan Urea
4

 Bio-Fertilizers

WATER CHEMISTRY OVERVIEW

Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state (water vapour or steam). Water also exists in a liquid crystal state near hydrophilic surfaces. Under nomenclature used to name chemical compounds, Dihydrogen monoxide is the scientific name for water, though it is almost never used. Water covers 70.9% of the Earth's surface and is vital for all known forms of life. On Earth, 96.5% of the planet's water is found in oceans, 1.7% in groundwater, 1.7% in glaciers and the ice caps of Antarctica and Greenland, a small fraction in other large water bodies, and 0.001% in the air as vapour, clouds (formed of solid and liquid water particles suspended in air), and precipitation. Only 2.5% of the Earth's water is freshwater, and 98.8% of that water is in ice and groundwater. Less than 0.3% of all freshwater is in rivers, lakes, and the atmosphere, and an even smaller amount of the Earth's freshwater (0.003%) is contained within biological bodies and manufactured products. Water on Earth moves continually through the hydrological cycle of evaporation and transpiration (evapotranspiration), condensation, precipitation, and runoff, usually reaching the sea. Evaporation and transpiration contribute to the precipitation over land. Uses of Water in an industry:i.) ii.) iii.) Water is used as a coolant. Water is used as a solvent. Raw Water is used to prepare Demineralised (DM) water for the preparation of steam in boilers, for make-up and analysis in Laboratories. To create Hydraulic pressure in plant processes. As a chemical reactant. To obtain hydrogen (which is present as 2 parts in 1 part water).
5

iv.) v.) vi.)

Q. HOW WATER BECOMES IMPURE? Water is one of the basic requirements in production of steam. In nature water is available in abundance. Its physical and chemical characteristics vary depending upon the source and strata on which it flows. It picks up mineral salts from the soil, which go in to solution. Water, therefore contains mineral salts in dissolved condition, in varying proportions, composition and degree. It gets polluted further with multifarious organic and in organic impurities due to disposal of industrial and domestic wastes. Decayed vegetation and micro-organism also contribute to contamination. Water also contains coarse substance in suspended form, constituting of silt and clay matters, generally termed as turbidity. Silicate matters are present in dissolved as well as in colloidal forms, proportion of which varies depending mainly on the following conditions: Temperature Seasonal Conditions Chemical characteristics of the particulate Velocity of the flow.

TYPE OF IMPURITIES Dissolved mineral matters present in water are composed of metallic Component (cations) and acidic component (anions) in equal quantity of Positively charged cations & negatively charged anion.

Ionic &Dissolved Cationic Calcium Anionic Bicarbonate

Non-ionic And Undissolved Turbidity, Silt Mud ,Dirt And Other Suspended Matters. Colour Organic Matter Colloidal Silica

Gaseous Carbon Dioxide Hydrogen Sulphide

Magnesium Sodium Potassium Ammonium Iron Manganese

Carbonate Hydroxide Sulphate Chloride Phosphate Bisilicate (HSiO3), Silicate (SiO3), Silicic Acid (H2SiO3)

Methane Oxygen Chlorine

Micro-organism Plankton, Bacteria

Organic Matter

Oil And Corrosion Products

SOLUBLE AND SUSPENDED IMPURITIES FOUND IN WATER AND THEIR FFFECTS:Constituent Chemical formula None. Expressed In analysis as units Difficulties caused Means of treatment Coagulation, settling, and filtration

1. Turbidity

Imparts unsightly appearance to water; deposits in water lines, Process equipment, etc. Chief source of scale in heat exchange equipment, boilers, pipe lines, etc.; Forms curds with soap, Interferes with dyeing, etc. Corrosion in water lines, particularly steam and condensate lines

2. Hardness

calcium and magnesiu m salts, expressed as CaCO3 CO2

Softening; demineralizatio n; internal boiler water treatment; surface active agents Aeration, deaeration, neutralization with alkalis Demineralizatio n, reverse osmosis, electro dialysis, evaporation

3. Carbon dioxide

4. Sulphate

SO42-

5. Fluoride

F-

Adds to solids content of water, but in itself is not usually significant, combines with calcium to form calcium sulphate scale Cause of mottled enamel in teeth; also used for control
8

Adsorption with magnesium hydroxide, calcium

6. Sodium

Na+

7. Iron

Fe2+ (ferrous) Fe3+ (ferric)

of dental decay: not usually significant industrially Adds to solids content of water: when combined with OH-, causes corrosion in boilers under certain conditions Discolours water on precipitation; source of deposits in water lines, boilers etc.; Interferes with dyeing, tanning, papermaking, etc.

phosphate, or bone black; alum coagulation Demineralizatio n, reverse osmosis, electrodialysis, evaporation

8. Manganese 9. Oxygen

Mn2+ O2

Same as iron Corrosion of water lines, heat exchange equipment, boilers, return lines, etc. Cause of "rotten egg" odour. Corrosion

Aeration; coagulation and filtration; lime softening; cation exchange; contact filtration; surface active agents for iron retention Same as iron Deaeration; sodium sulphite; corrosion inhibitors Aeration; chlorination; highly basic anion exchange Cation exchange with Hydrogen zeolite; chlorination; Lime softening and cation

10. Hydrogen sulphide

H2S

11. Ammonia

NH3

Corrosion of copper and zinc alloys by formation of complex soluble ion Refers to total amount of dissolved
9

12. Dissolved solids

None

matter, determined by evaporation; high concentrations are objectionable because of process interference and as a cause of foaming in boilers 13. Suspended solids None Refers to the measure of undissolved matter, determined gravimetrically; deposits in heat exchange equipment, boilers, water lines, etc. Refers to the sum of dissolved and suspended solids, determined gravimetrically Corrosion

exchange by hydrogen zeolite; demineralizatio n, reverse osmosis, electro dialysis, evaporation Subsidence; filtration, usually preceded by coagulation and settling

14. Total solids

None

See "dissolved solids" and "suspended solids" Neutralization with alkalis

15. Free mineral Acid

H2SO4 , HCl etc., expressed as CaCO3 NO3-

16.

Nitrate

Adds to solids content, but is not usually significant industrially, high concentrations cause methemoglobinemia in infants; useful for control of boiler metal embrittlement Adds to solids content and increases corrosive character of water
10

Demineralizatio n, reverse osmosis, electro dialysis, evaporation

18. Chloride

Cl-

Demineralizatio n, reverse osmosis, electro dialysis,

19. Alkalinity

evaporation. Bicarbonat Foam and carryover Lime and limee of solids with soda (HCO3 steam; embrittlement softening; acid -), of boiler treatment; carbonate steel; bicarbonate hydrogen zeolite (CO3 and carbonate softening; 2-), produce co2 in steam, demineralizatio and a source of n hydroxide corrosion in dealkalization (OH-), condensate lines by anion expressed exchange as CaCO3 Al3+ Usually present as a result of floc carryover from clarifier; can cause deposits in cooling systems and contribute to complex boiler scales. Scale in boilers and cooling water systems; insoluble turbine blade deposits due to silica vaporization Improved clarifier and filter operation

20. Aluminium

21. Silica

SiO2

Hot and warm process removal by magnesium salts; adsorption by highly basic anion Exchange resins.

11

PRE-TREATMENT PLANT Introduction Water flowing through canal from Gopi Krishna Sagar enters the canal water pump sump. Prior to this, it passes MS vertical bar screen, where in floating substances are arrested, which are removed whenever required by lifting these screen by means of chain pulley block provided. A provision of MS gate has also been made in order to stop the flow of water into canal water sump pumps during any maintenance or repairing work. Also it stops the flow of water from the canal sump to the canal when the water is drawn from the raw water storage tanks. At one end of canal water sump, pump house accommodates four pumps with motors and control valves. Provision for fifth pump has also been provided. During normal operation three pumps will be working at a time, transmitting a flow of 1500 m3/hr to raw water storage for circulation and 3000 m3/hr to the pre-treatment. An interconnecting line along with electrically operated electrically operated butterfly valve and manually operated butterfly valve has been provided between raw water storage tank and canal water sump. When the level in canal water sump goes below the low water level, the electrically operated butterfly valve opens and water starts flowing from raw water storage tank starts flowing from the raw water storage tank into the canal water sump to maintain the required level there. Water flowing to the plant is conveyed through 800/1000 diameter MS pipeline. Flow of water coming from the canal water pump is controlled by means of 800 mm electrically operated butterfly valve provided in the upstream of the chlorine contact vessel.

PURPOSE OF AERATION Aeration is necessary to promote the exchange of gases between the water and the atmosphere. In this plant it is provided for the following purpose:

1. To add oxygen to water for imparting freshness

12

2. Expulsion of chlorine and other volatile substance 3. To precipitate impurities like iron and manganese in certain forms To ensure proper aeration, cascade type aerator is provided. In this type water is discharged through a riser pipe and distributed on to a series of steps through which the water falls in thin film to the base of the collection basin. From here water passes through partial Flume to the flash mixers.

CHEMICAL DOSING In this treatment plant following treatments is given: 1. Pre-chlorination by chlorine solution dosing in chlorine contact vessel 2. Coagulation by alum and PAC solution dosing for the main stream and the demineralization stream water at the downstream side of the aerator 3. pH correction by lime solution dosing at the downstream side of the aerator 4. Post-chlorination by chlorine solution dosing for sanitary water only in the sanitary water reservoir. 5. Chlorination by bleaching powder dosing as alternative chlorine dosing. PURPOSE OF ALUM DOSING

This is used for coagulation. It is a process for combining or flocculating the colloidal or larger particles of suspended matters so that they are more readily settled out of the water and filtered out effectively with a minimum of resistance when trapped as sand bed. There is one specific pH zone of water in which good flocculation occurs in the shortest time with a good dose of coagulant. In case of water containing low mineral contents or in the presence of interfering organic matters while dosing alum constant attention is needed.

13

 PURPOSE OF LIME DOSING In the case of coagulation with alum, the control over the alkalinity is very important. Not only should the water contain sufficient alkalinity to completely react with the aluminium sulphate but there should be a sufficient residual to ensure that the treated water is not corrosive. Reduction of alkalinity should be taken into consideration and sufficient alkalinity should be added to water if necessary. For this purpose, hydrated lime, Ca(OH)2 is use here.

PURPOSE OF CHLORINATION

Chlorination is an important disinfectant for drinking water and waste water. Pre-chlorination in the application of chlorine to water prior to any unit treatment process is for control of biological growths in raw water line, promotion of improved coagulation, prevention of mud ball and slime formation in filters, reduction of taste, odour and colour and minimize the postchlorination dosages. Post-chlorination in the application of chlorine to filtered water before it enters the distribution system for disinfection by maintaining the required amount of free chlorine.

FLASH MIXERS Process and purpose Flash mixing is an operation by which the coagulant is rapidly and uniformly dispersed throughout the mass of water. This helps in the formation of micro flocs and results in proper utilization of chemical coagulant preventing localization of concentration and premature formation of hydroxides which lead to less effective utilization of the coagulant. In this plant the chemical coagulant that is alum is dosed in the both streams flash mixing tanks. Lime solution is also added in the both stream flash mixer for correcting the pH value of water. For draining the Flash mixer tanks, a provision of 100 mm diameter sluice valve with extension spindles is made.
14

CLARIFLOCCULATORS Working The coagulated water from Flash Mixer is introduced through the hollow center pair of the clariflocculator tank. It enters the flocculator compartment below the liquid surface through opening in the center pier. Here the specially designed paddles produces a gentle controllable motion to provide the most effective contacting between the newly formed flocs and the incoming liquid without damaging the flocs system . By this section the flocs are given intimate impact with the finely divided particles, which are thereby scrubbed out of suspension. The completely flocculated liquid flows through the opening in the bottom of the flocculator tank into the clarifier compartment where the flocs are given sufficient time to settle down. In this case we have considered this time as 2.5 hours. The settled solids are being conveyed to the central sludge collection sump by means of scrapper blades attached to the paddles arms for discharge into the clarifier drain sump. General description and working Candy Filter Floor essentially consists of rows of earthenware pipes having holes at regular intervals to accommodate Candy Filter nozzles and embedded in concrete. Once the filter floor is laid, the nozzles are screwed into the respective nozzles holes. Over this filter floor the filter media of about 850 mm depth of graded sand will be filled. During normal filtration process, the inlet and the outlet valves are in open position and rest of the valves are in closed position. The settled water having turbidity not more than 20 ppm first enters into wash water and then overflows over the filter media and the water after filtration passes through the outlet. During the filtration process the suspended matter and other impurities in the water are retained on the top of the sand bed. The amounts of the chemicals used, their dose, and point of application are tabulated below:
15

Name of Chemical

Dose (ppm)

Point of application

Flow Chemicals rate of required water (kg-s/hr) (m3/hr )

Chemical solution flow rate (LPH)

Solution strength/ solution ratio Purpose

Chlorine :for prechlorination 5

Chlorine Contact Vessel 3000 15 15000 0.1% Disinfect ion

Alum

50

Downstrea m Side of aerator

3000

150

1500

10%

Coagulat ion pH correctio n

Lime 30 Chlorine :for postchlorination Bleaching Powder (alternative to chlorine dosing for postchlorination) 2 2

Downstrea m side of aerator Sanitary water reservoir Sanitary water reservoir

3000

90

1800

5%

300

0.6

600

0.1%

Disinfect ion

300

3.6

109

3.3%

Disinfect ion

16

DEMINERALISATION PLANT

1. Treatment Scheme The steps followed in the demineralization of water are as follows:

1. The filtered water is passed through heat exchanger with a view to cool the condensate coming from the turbine and process so that condensate with reduced temperature can be treated in condensate plant. 2. Removal of excess chlorine in filtered water by passing through activated carbon filter. 3. Removal of positive ions by passing through a pair of weakly acidic (WAC) and strongly acidic (SAC) exchangers. 4. Removal of CO2 present in decationised water in atmospheric forced draft type degassers. 5. Removal of negative ions by passing through a pair of weakly basic (WBA) and strongly basic (SBA) anion exchangers. 6. Passing SBA treated water through mixed bed exchanger (MB) to polish off remaining ions to get ultra-pure water. Regeneration of the ion exchangers is carried out when the treated water quality is not satisfactory or when the unit has delivered its specified output between the regenerations, whichever is earlier. The SAC and WAC are regenerated with sulphuric acid using thoroughfare regeneration technique. Caustic solution is used for the regeneration of WBA and SBA units using thoroughfare technique. Caustic for SBA and WBA is injected at approximately 45 C using heat exchanger with a view to obtain low silica residual from SBA units. Counter-current technique is employed for regeneration of SAC with a view to minimize sodium ion slippage from SAC outlet. For MB, resins are first separated, and then anion resin is regenerated with alkali and cation with acid. Injection of acid from bottom and alkali from top is carried out simultaneously. The resultant effluent is drained through the middle collector. As MB units act as a polisher, the same to be taken up for regeneration once the specified quantity of water has been treated.

17

Neutralization pit comprising of three compartments and lined with acid proof material is provided for collection of effluent coming out during regeneration of exchanger units. Acidic effluent coming out during cation regeneration is collected in the first section of the pit. Alkali effluent coming out during anion regeneration is collected in the third section of the pit. The acidic and alkaline effluents are discharged separately to the main effluent plant or they are discharged to the center pit for neutralization. As the resultant effluent will be acidic, lime or caustic is added to neutral the effluent to the required pH between 6 and 8. Mixing in center pit is carried out by air agitation and the effluent is re-circulated till the desired pH is obtained. Thereafter the effluent is discharged to the storm water drain.

2. DESCRIPTION:The de-mineralized water treatment plants consist of three chains in parallel each comprising: 1. ACF, WAC/SAC, WBA/SBA and MB exchangers, 1. 3 Nos. of filtered water pumps, 2 Nos. atmospheric degassers, 2. 1 Nos. degassed water tank, 3. 5 Nos. degassed water pumps (3 Nos. for service and 2 Nos. for regeneration) and, 4. 2 Nos. DM water storage tanks. From DMWT SBA treated water is pumped with the help of DM water pump through MB and stored in polished water storage tank. pH correction of polished water storage tank is done with ammonia solution dosing pump before the polished water is discharged to the end use by means of polished water pumps.

18

 ACTIVATED CARBON FILTER

It is a mild steel vessel painted internally with epoxy based paint. It is externally fitted with MS pipe-work, diaphragm and butterfly valves, pressure gauge at the inlet and sampling valves both at the inlet and outlet, DPI is provided to check the pressure drop across the carbon bed. An alarm will be sounded in case the pressure drop across the bed increases beyond the set limit. A calibrated orifice board in the drain sump is also provided for controlling the backwash flow rate. Mild steel, epoxy painted both internally and externally, bell mouth type single arm distributor is provided for inlet. This distributor becomes outlet during backwash operation. Bottom collecting system is of header lateral type. Header is of mild steel painted externally and internally with epoxy. To this header are screwed PVC laterals. There are small holes drilled throughout the length of the laterals. With a view to obtain a horizontal surface, the bottom-dished end is filled with concrete. With a view to ensure that the carbon does not leak through the bottom collecting system, different layers of under bed materials are charged. Each layer consists of different size of pebbles with bigger size at the bottom most and fine silex on top. Above fine silex, activated carbon is charged. Rate of flow indicator is provided at the inlet to check the hourly flow rate.

Regeneration is done in two stages:

1. Backwash This operation is carried out to loosen the bed and remove suspended impurities. 2. Rinse This operation is carried out to ascertain that the performance of the unit with respect to quality is in order.

19

 WEAK ACID CATION UNITS (WAC)

This is a mild steel vessel lined internally with rubber. It is externally fitted with rubber lined pipe-work, diaphragm and butterfly valves, pressure gauge at the inlet and sampling valves both at the inlet and outlet, DPI is provided to check the pressure drop across the bed. A calibrated orifice board in the drain sump is also provided for controlling various regeneration flows. Inlet water distribution is of three arms. The water is distributed from the top and each arm is provided with PVC perforated pipes for uniform distribution. Backwash outlet is provided separately internally which essentially consists of rubber lined rubber covered bell mouth. Acid distributor is also of three arms made out of mild steel and lined internally as well as externally with rubber. Bottom collecting system is of header lateral type. It consists of mild steel rubber lined and rubber- covered header into which mark V strainers are fitted. The vessel is charged with weakly acid cation resin. The regeneration of the unit is done in thoroughfare with SAC. Flow indicator totalizer is provided at the outlet and a rate off low indicator is provided at the inlet.

STRONG ACID CATIONS UNIT (SAC)

This is a mild steel vessel lined internally with rubber. It is externally fitted with rubber lined pipe-work, diaphragm and butterfly valves, pressure gauge at the inlet and sampling valves both at the inlet and outlet, DPI is provided to check the pressure drop across the bed. A calibrated orifice board in the drain sump is also provided for controlling various regeneration flows. Regeneration of SAC and WAC is carried out simultaneously. The regeneration is carried out in five stages.
20

1. Backwash / Sub-surface wash Backwash operation is carried out to loosen the bed and to remove the suspended impurities from the resin. The operation is carried out independently. For SAC sub-surface wash is carried out. Backwash operation for SAC is optional and should be carried out once in 15 regenerations or when pressure drop across the unit increases beyond acceptable limits whichever occurs earlier. When backwash is given to SAC, double quantity of acid is to be injected to ensure that bottom layer of the resin is highly regenerated.

2. Settle Backwash resins are allowed to settle under gravity to get uniform resin surface.

3. Acid Pre-injection This operation is carried out to set the power flow rate to the required flow before injecting acid. 4. Acid injection Acid of required strength and quantity is injected into SAC and WAC by injection pump. The acid is injected in SAC and the effluent from the middle collector is passed through WAC unit. The effluent is collected in the drain sump. During injection to prevent the fluidization of SAC bed, a down-flow of water is maintained.

5. Acid transfer To ensure optimum utilization of acid this operation is carried out. The excess acid in the SAC unit after acid injection is transferred to WAC with the help of power water. Down-flow of water is maintained during this stage also. Inlet water distributor is of three arms. The water is distributed from the top and each arm is provided with PVC perforated pipe for uniform distribution. Backwash outlet is provided separately internally which essentially consists of rubber lined rubber covered bell mouth. Bottom dished portion of the vessel is fitted with concrete which
21

acts as dead weight and thus prevents the divisional plate from getting buckled due to the weight of water and resin. The vessel is charged with strong acid cation resin when the desired output from the pair of units (WAC and SAC) is obtained or when the quality of outlet water from the SAC with respect to sodium ions is deteriorated then the unit should be regenerated in thoroughfare with WAC using H2SO4 as regenerant. A resin trap with DPI is provided to trap ion exchange resins in the unlikely event of failure of the bottom collecting system. A conductivity comparator is provided at the outlet of the unit comprising of two conductivity cells and a comparator.

6. Rinse This operation is carried out to remove excess acid and liberated cations from both WAC/SAC units. This operation is carried out simultaneously but independently.

7. Backwash As WAC resin gets compact due to contraction after regeneration, this operation is carried out for 2 minutes to loosen the bed.

22

 WEAK BASE ANION (WBA) This is a mild steel vessel lined internally with rubber. It is externally fitted with rubber lined pipe-work, diaphragm and butterfly valves, pressure gauge at the inlet and sampling valves both at the inlet and outlet. DPI is provided to check the pressure drop across the bed. A calibrated orifice board in the drain sump is also provided for controlling various regeneration flows. Inlet water distributor is of three arms. The water is distributed from the top and each arm is provided with PVC perforated pipe for uniform distribution. Backwash outlet is provided separately internally which essentially consists of rubber lined rubber covered bell mouth with SS mesh fixed on it to prevent resin carryover. Alkali distributor is also of three arms and made of mild steel and lined internally as well as externally with rubber. Bottom collecting system is of header lateral type. It consists of mild steel rubber lined and rubber covered header into which PVC laterals with mark V strainers are fitted. The vessel is charged with weak base anion resin. The unit is regenerated in thoroughfare with SBA. A resin trap with DPI is provided to trap ion exchange resins in the unlikely event of failure of the bottom collecting system. Rate of flow indicator is provided at the inlet and outlet.

STRONG BASE ANION UNIT (SBA)

It is a mild steel vessel lined internally with rubber. It is externally fitted with rubber lined pipework, diaphragm and butterfly valves, pressure gauge at the inlet and sampling valves both at the inlet and outlet. DPI is provided to check the pressure drop across the bed. A calibrated orifice board in the drain sump is also provided for controlling various regeneration flows.

23

Inlet water distributor is of three arms. The water is distributed from the top and each arm is provided with PVC perforated pipe for uniform distribution. Backwash outlet is provided separately internally which essentially consists of rubber lined rubber covered bell mouth with SS mesh fixed on it to prevent resin carryover. Alkali distributor is also of three arms and made of mild steel and lined internally as well as externally with rubber. Bottom collecting system is of header lateral type. It consists of mild steel rubber lined and rubber covered header into which PVC laterals with mark V strainers are fitted. The vessel is charged with strongly basic anion resin. The unit is regenerated in thoroughfare with WBA using NaOH as regenerant, when the quality of treated water from SBA outlet with respect to silica is deteriorated. A resin trap with DPI is provided to trap ion exchange resins in the unlikely event of failure of the bottom collecting system. A conductivity indicator is provided at the outlet of the unit to give alarm in case the conductivity increases beyond the acceptable limit. Flow indicator is provided at the outlet. Regeneration of SBA and WBA is carried out simultaneously. The regeneration is carried out in six stages: 1. Backwash Backwash operation is carried out to loosen the bed and to remove the suspended impurities from the resin.

2. Settle Backwash resins are allowed to settle under gravity to get uniform resin surface.

24

3. Acid Pre-injection This operation is carried out to set the power flow rate to the required flow before injecting acid.

4. Acid injection Specified quantity of caustic is injected by means of primary and secondary rejecters to regenerate the exhausted resins.

5. Acid transfer To ensure optimum utilization of alkali this operation is carried out. The excess alkali in the SBA unit after caustic injection is transferred to WBA with the help of power water.

6. Rinse This operation is carried out to remove excess caustic and liberated anions from both WBA/SBA units. This operation is carried out simultaneously but independently.

25

 MIXED BED (MB)

It is a mild steel vessel lined internally with rubber. It is externally fitted with rubber lined pipework, diaphragm and butterfly valves, pressure gauge at the inlet and sampling valves both at the inlet and outlet. DPI is provided to check the pressure drop across the bed. A calibrated orifice board in the drain sump is also provided for controlling various regeneration flows. Inlet water distributor is of three arms. The water is distributed from the top and each arm is provided with PVC perforated pipe for uniform distribution. Backwash outlet is provided separately internally which essentially consists of rubber lined rubber covered bell mouth with SS mesh fixed on it to prevent resin carryover. The middle collector and bottom collecting system are of header lateral type. The header is of mild steel rubber lined and rubber covered to which PVC laterals are fitted. Mark V strainers are used for the bottom collecting system and mark 801 is used for the middle collecting system. Bottom dished portion of the vessel is fitted with concrete to prevent the divisional plate from getting buckled due to the weight of water and resin. The vessel is charged with a mixture of both strongly acidic cation resin and strongly basic resin. When the desired output from the unit is obtained or when the quality of outlet water with respect to either silica or conductivity is deteriorated then the unit should be regenerated, cation resin with H2SO4 and anion resin with NaOH. A resin trap with DPI is provided to trap ion exchange resins in the unlikely event of failure of the bottom collecting system. In addition to rate of flow indicator provided at the unit inlet, following instruments are provided at the MB outlet: (1) Conductivity indicator to give alarm in case the treated water conductivity increase beyond the acceptable limit. (2) pH indicator to give alarm for both low and high pH
26

(3) Flow indicator/totalizer to determine the quantity of water treated between successive regenerations. (4) Silica analyser with multiposition switch is provided at common outlet to give alarm. (5) At common rinse outlet line conductivity indicator is provided to give alarm once acceptable limit is obtained.

Regeneration of MB is carried out in 13 stages: 1. Backwash This operation is carried out to separate the resin beds prior to injecting the chemicals. Due to difference in densities, the resins during backwash get separated into two distinct layers with cations being at the bottom and anions at the top.

2. Sub-surface wash This operation is basically carried out to clean the middle collector strainers to ensure proper distribution/collection during injection of chemicals. 3. Settle Resins after backwash and sub-surface wash are allowed to settle under gravity to obtain uniform bed surface.

4. Acid and Alkali pre-injection This operation is carried out to set the power water flow rates before starting the injection of both acid and alkali.

5. Acid and Alkali injection

27

Injection of acid and alkali is carried out simultaneously. Acid from the bottom and alkali from top and the resultant effluent is drained through the middle collector. The purpose of regeneration is to regenerate the exhausted resins.

6. Acid and alkali rinse This operation is carried out simultaneously to remove excess regenerants from respective resin beds.

7. Drain down With a view to reduce excess load on air blower, excess water in MB vessel is drained through the middle collector. The purpose of the injection is to regenerate the exhausted resins.

8. Air mix This operation is carried out to mix the two resins. This operation is very important as improper mixing will lead to inferior treated water quality. Air mixing is carried out with the help of blowers.

9. Force settle In order to prevent the resins from getting separated after mixing, this operation is carried out.

10. Refill-1 This operation is carried out to fill the MB units with water.

11. Refill-2 This operation is carried out to release air and to pressurize MB unit.
28

12. Rinse to drain This operation is carried out to remove the traces of acid/alkali from the mixed bed. 13. Final rinse recycle This operation is carried out to reduce the wastage of DM water whose quality though not of acceptable quality is good enough to be recycled back into DM water storage tank. Once water of acceptable quality is obtained during recycle operation the unit is taken in service to fill the polished water storage tank.

29

RESINS USED IN DEMINERALISATION PROCESS In the demineralization of water wide variety of resins are used. However, resins most commonly used are indicated below:

1. Strong acid cation exchange resin This is a sulphonated cross-linked styrene/ di-vinyl benzene polymer. These are available in the form of beads of size ranging between 0.3 mm and 1.2mm and total exchange capacity of 2 to 2.2 milli-equivalents per ml. These are normally quite stable at all pH range and against normal chemicals encountered in water. These resins can be regenerated by the use of strong acid like hydrochloric acid, sulphuric acid, and nitric acid. The operating capacity normally lies between 3070 grams per litre depending on regeneration level and water characteristics. Regeneration efficiency varies between 0.3 to 0.45 under normal co-current regeneration. Reactions involved in the treatment of water and regenerations are as follows:

Exhaustion reaction: RH + M(Cl, SO4, NO3, CO3, HCO3, SiO2) RM + (HCl, H2SO4, HNO3, H2CO3, H2SiO3)

Regeneration reaction: RM + (HCl, H2SO4, HNO3) R Resin phase M Cation RH + M(Cl, SO4, NO3)

30

2. Weak acid cation resin These are copolymers of acrylic acids and di-vinyl benzene having active carboxylic group. The resins are obtained in the form of beads of sizes 0.3 mm to 1.2 mm having total exchange capacity of 3-4 milli equivalents per ml. These resins can react only with the alkalinity of water with the production of carbonic acids. The regeneration can be done by any acid using slightly more than the stoichiometric quantity. The operating capacity depends on the period of exhaustion and water characteristics and lies between 30100 grams per litre. The reactions involved with these resins are as follows:

Exhaustion reaction: 2RCOOH + MCO3 RCOOM + H2CO3

Regeneration reaction: RCOOM + (HCl, H2SO4, HNO3) RCOOH + M(Cl,SO4, NO3)

3.

Strong base anion resin (Type-1)

These are quaternary ammonium compounds of resin obtained from cross- linked styrene di-vinyl benzene by amination. These are obtained in the form of beads between 0.3 to 1.2 mm of size and total exchange capacity of 1.2 milli equivalent per ml. These resins can react with free acids (including weak acid like silicic and carbonic acid) with the production of water. This can also react with neutral salts absorbing the anions and producing the corresponding hydroxide. Regeneration of this resin can be carried out by use of sodium hydroxide. The operating capacity depends on the regeneration level and the characteristics of water and normally ranges from 20 to 30 grams per litre. Reactions involved with these resins are as follows:

31

Exhaustion reaction: ROH + (HCl, H2SO4, HNO3, H2CO3, H2SiO3) R(Cl, SO4, NO3, HCO3, HSiO3) + H2O

Regeneration reaction: R(Cl, SO4, NO3, HCO3, HSiO3) + NaOH ROH + Na(Cl, SO4, NO3, SiO3, CO3)

4. Strong base anion resin (Type-2) These are obtained in the same manner as a type-1 resin only in the quaternary ammonium group an alkanol group is present. These have got a capacity of 1.2 milli equivalent per ml and operating capacity are higher than that of type-1 resins ranging between 30 to 45 grams per litre. However, the efficiency of removal of weak acid is less than that of type-1 resins, but there generation efficiency is higher.

5. Weak base anion exchange resins These are prepared in the same manner as strong base resins from styrene di-vinyl benzene co-polymer, only amination is carried on by primary or secondary amine so that a tertiary ammonium compound is obtained. These are also obtained in the form of bead of 0.3 to 1.2 mm having exchange capacity up to 1.6 milli equivalent per ml. Because of low basicity they can absorb only free strong acids but they cannot remove weak acid or react with neutral salts. The regeneration efficiency is very high and only stoichiometric quantity of alkali is required for its regeneration. These resins can be regenerated by caustic soda, sodium carbonate or even by ammonia. The reactions involved are: Exhaustion reaction:
32

RN + H(Cl, SO4, NO3) Regeneration reaction:

RN(HCl, H2SO4,HNO3)

RN(HCl,H2SO4,HNO3) + NaOH

RN + Na(Cl,SO4,NO3) + H2O

Resins described above are used in the gel form normally but isoporous and macroporous forms of these resins are also available and can be used where they are required. A judicious selection of the resin is the primary requirement in the design of a demineralization system.

33

CAPTIVE POWER PLANT The CPP unit in NFL deals of with two tasks: (i) (ii) Power Generation Steam generation

Here, I have given outline of the Steam generation process of the CPP.
BOILER OPERATION: Operation modesHeat recovery unit (HRU) in conjunction with gas turbine generator (GTG) is composed of the following operation modes. 1. Steady operation modes (a) Stop mode HRU is in stop mode and all dampers are so positioned as to allow GTG to operate in open cycle condition. (b) Cogeneration mode GTG exhaust gas is introduced to HRU and HRU generates HP steam with supplementary fuel. (c) FDF operation mode FD fan is adopted, in place of GTG to supply combustion air and HRU generates HP steam only by fuel firing.

2. Operation mode change between above mentioned modes involve automatic sequence control as follows: (a) Start-up modes : From (a) to (b), hot/cold start-up modes by GTG exhaust gas : From (a) to (c), start-up mode by FDF (b) Change over modes : From (b) to (c), change over mode automatically initiated by GTG trip

34

: From (c) to (b), change over mode manually initiated by push button switch (c) Shut down modes : Scheduled/Emergency shutdown modes have priority over other modes.

Fig. NG based Thermal power Plant.

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DESCRIPTION OF HEAT RECOVERY UNIT

The boiler of the heat recovery unit is of KAWASAKI type natural circulation, two drums, water-tube, self-standing and front firing boiler which consists of steam drum, water drum, furnace, super heater, convection tube bank, economizer, inter-connecting flue gas duct, stack and the associated equipment. BOILER PARTS 1. STEAM DRUM Steam drum has sufficient capacity for separating maximum generating steam and has sufficient capacity to minimize water level fluctuation resulting from start and stop or quick load change. The construction of the steam drum is of boiler steel plate fusion welded longitudinal and circumferential seams are automatically welded by an electric arc welding process. One round manhole with a hinged cover is provided at each ortho-ellipsoidal end plate of the drum. The steam drum is fitted with steams separating internals and chevron dryer, which are designed to assure high purity in every load. The wet steam entering the drum from the riser tubes is collected in a small compartment formed by the internal baffles and dry steam is separated through the separator connected at the top section of this compartment, so as not to mix the generating steam into drum water. This is essential for the design of minimizing the water level fluctuation in steam drum. Steam drum id fitted with other internals of feed water distribution pipe, chemical feed pipe and continuous blow down pipe. All pipe connections on the drum are welded.

2. WATER DRUM The construction of the steam drum is of boiler steel plate fusion welded. The longitudinal and circumferential seams are automatically welded by an electric arc welding process. One round

36

manhole with a hinged cover is provided at each ortho-ellipsoidal end plate of the drum. The water drum serves as mud drum and is fitted with bottom blow nozzles. For heating up of boiler, steam injection nozzle is equipped in this drum.

3. FURNACE Furnace has sufficient size for burning fuel gas as basic design and fuel oil in future plan. For the furnace wall, Tight Wall- totally welded gas tight membrane tube wall is employed. Where the tubes penetrate the wall, all gaps are completely sealed with seal plate and sleeves of tube elements.

4. SUPERHEATER A convection super heater is installed in the high temperature gas area in the fore front of the convection tube bank. Since super heater tubes are installed in the convection area, radiation heat from the furnace can be intercepted. And therefore, thermal load on the superheating tubes is limited in the reasonable range and overheating or damage by burning of the tubes is totally prevented at the boiler start or its partial operation. Super heater tubes are of bare tubes and are arranged in triangular pitch, vertical run and serpentine pattern. Steam temperature at the outlet of the superheater is controlled through de-superheating by means of boiler feed water in the steam flow.

5. CONVECTION TUBE BANK Convection tube bank has compact heating surface divided into three sections by two baffle plates which are employed for turning over gas
37

flow. Convection tubes are of bare tubes and are arranged in line and vertical run. Each tube is completely joined to steam drum and water drum by expanding.

6. ECONOMIZER The economizer is located behind the convection tube bank. The arrangement of the tube is in triangular pitch. Its tubes are spiral-finned tubes which are welded by high frequency resistance welding process. Spiral fin tubes have sufficient fin spacing considering not only gas firing but, fuel oil firing condition in future. The economizer is divided in upper tube bank and lower tube bank. The boiler feed water is supplied to the bottom header of upper tube bank of economizer, flows upward and is corrected in the top side header. And the corrected water is supplied for further heating up to the bottom header of lower tube bank of economizer, flows upward and is corrected in the top side header. Above flow pattern is employed to serve steady water flow so as to eliminate the problems of steam vapour lock and air lock in tubes.

OPERATION AND MAINTENANCE The boiler possesses a number of advantages in maintenance as follows: 1. Because of tight wall construction, the wall of the furnace never suffers from damages and thus no repair work is required. 2. Because the burner cone is covered with many water tubes, repairing of refractories of the burner cone is hardly required. As an adequate air pressure head is provided, air distribution to the respective burners can be made uniformly, thus eliminating the possibility of damaging the burner. 3. Drain valves and blow valves of the boiler are gathered at one position on the side of the boiler for facilitating the operation of the boiler. 4. Adequate working spaces and manholes are provided for easy maintenance.

38

CRITICAL FAILURES OF BOILER If a critical failure as shown below develops, immediately shut off the fuel and follow the emergency shutdown procedure without hesitation. 1. Water level of the drum is reduced below the lower limit. 2. Fuel pressure drops below the lower limit and rises above the upper limit. 3. Oil atomizing press drops below lower limit & rises above the upper limit. 4. Forced draft fan is stopped. 5. Control air pressure is reduced below the lower limit. 6. Flame failure of all burners. 7. Power supply failure. 8. Steam pressure rises above the upper limit. 9. All seal air fans are stopped. 10.GTG exhaust gas pressure rises above the upper limit. 11.Each damper is actuated toward normal position under any operation mode. 12.Water quality is worsening suddenly. 13.Burner flames are blown out. 14.Combustible gas in the furnace is detonated. 15.Any boiler tube is busted. MINOR FAILURES OF BOILER Operators may encounter various abnormal conditions not as serious as the above critical failures. Boiler may be shut down depending on the conditions, even if a minor failure is detected.

COMBUSTION CONTROL Air more than theoretically required is needed for the complete combustion of fuel. The amount of air exceeding the required air is called excess air. It is desirable to minimize excess air not to disturb complete combustion, in view of thermal economy, low temperature corrosion prevention or power saving. Thus, it is important to set, correct and adjust air-fuel ratio for maintaining optimum combustion according to the combustion condition, exhaust gas analysis and smoke discharged from stack. Excess air factor varies according to the kind of fuel.
39

WATER QUALITY CONTROL Among accidents occurred during the boiler operation, the trouble resulted from the quality control of the water is one of the most serious accidents. Interests in the quality control of the boiler water have soared up. Parameters of water quality control:1. pH As well known, pH is an index showing acidity and alkalinity. For purified water or neutral solution, pH is 7, for acidic solution pH is less than 7 and for alkaline solution pH is more than 7. Since, iron as main construction material is soluble not only into acidic water but also into neutral water, pH of boiler must be raised a little in orders to minimize corrosion. But there is a limit to this as higher pH may cause alkaline corrosion as stronger alkalinity gives injurious effects on iron and especially on copper alloy, so there is an upper limit to pH of feed water. 2. Hardness Hardness in this criterion is a quantity in ppm of calcium carbonate equivalent to that of calcium and magnesium dissolved in water. Sticking of scales on the inside of the drum and heating tubes or deposits of sludge are mainly caused by this hardness component. These scale and sludge will result in a loss of boiler efficiency through worsened heat transfer. 3. Fats Fats inside of boiler, adhere to the heating surface, are heated, carbonized and invite a tube burst resulting from overheat due to the inability of fatty layer to conduct heat properly. 4. Dissolved oxygen Dissolved oxygen is one of the most injurious corrosive factors in boiler and its corrosion is very complicated, generally the progress of corrosion is considered due to the formation of oxygen concentration cell or destruction of ionic equilibrium in the solution.

40

5. Iron and Copper Most of the iron and copper contained in boiler water will become solids in suspension as hydroxides and oxides, and deposit on every surface because of their large specific weights. Precipitated and accumulated sludge obstruct the water circulation and also heat transfer, when depositing on the heating surfaces, causing an overheat and furthermore give the origin for the corrosion by concentration cell and the alkaline corrosion owing to formation of alkaline concentration layer based on local heating.

6. Silica The purpose of limiting the amounts of silica in the boiler water is first to prevent it from combining with calcium and magnesium when these are coexisting, precipitating and producing hard scale, and secondly to prevent the selective carry-over which would cause the silica in the boiler water to dissolve itself into the generated steam. CaO + SiO2 MgO + SiO2
heat heat

CaSiO3 MgSiO3

41

7. Alkalinity Alkalinity in boiler water is expressed in ppm of equivalent calcium carbonate (CaCO3) to acidic quantity, which is necessary for neutralizing the alkaline quantity in boiler water. In boiler water, appropriate amounts of NaOH must be included in order to make silica soluble, to give the generated sludge a floating nature and to produce a protecting film against corrosion over the iron surface. If these amounts however are in excess, they may cause caustic fragility of the steel material. 8. Total solids Total solids mean total residual substances from evaporation and are the sum of dissolved solids and suspended solids. In case, that amounts of total solids are larger in boiler water, carry-over is liable to occur, thus contaminating the generated steam owing to transfer of boiler water into the steam.

9. Chlorine ion Chlorine ion in boiler water destroys the protection film formed over the metal surfaces and delays its restoration. As the precipitation of these processes promotes corrosion, higher concentration makes its injuries larger.

10. Phosphoric ion If sodium phosphate is added to boiler water calcium phosphate of soft, floating nature would be generated and further generation of hard scale would be prevented. Nevertheless, excessive addition is not only un-economical but also accelerative in the foaming of boiler water which invite carry-over and easy to generate magnesium phosphate inside of tube.

42

AMMONIA PRODUCTION PROCESS AN OUTLINE

Ammonia is a compound of nitrogen and hydrogen with the formulaNH3. It is a colourless gas with a characteristic pungent odour. Ammonia contributes significantly to the nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers. Ammonia, either directly or indirectly, is also a building-block for the synthesis of many pharmaceuticals. Although in wide use, ammonia is both caustic and hazardous. In 2006, worldwide production was estimated at 146.5 million tonnes.[6] It is used in commercial cleaning products. Ammonia, as used commercially, is often called anhydrous ammonia. This term emphasizes the absence of water in the material. Because NH3 boils at 33.34 C (28.012 F) at a pressure of 1 atmosphere, the liquid must be stored under high pressure or at low temperature. "Household ammonia" or "ammonium hydroxide" is a solution of NH3 in water. The ammonia molecule has a trigonal pyramidal shape with a bond angle of 107.8, as predicted by the valence shell electron pair repulsion theory (VSEPR theory). The central nitrogen atom has five outer electrons with an additional electron from each hydrogen atom. This gives a total of eight electrons, or four electron pairs that are arranged tetrahedrally. Three of these electron pairs are used as bond pairs, which leaves one lone pair of electrons. The lone pair of electrons repel more strongly than bond pairs, therefore the bond angle is not 109.5, as expected for a regular tetrahedral arrangement, but is measured at 107.8. Ammonia is found in trace quantities in the atmosphere, being produced from the putrefaction (decay process) of nitrogenous animal and vegetable matter. Ammonia and ammonium salts are also found in small quantities in rainwater, whereas ammonium chloride (sal-ammoniac), and ammonium sulphate are found in volcanic districts; crystals of ammonium bicarbonate have been found in Patagonian guano. The kidneys secrete NH3 to neutralize excess acid.[8] Ammonium salts also are found distributed through all fertile soil and in seawater.

43

Ammonia is produced from a mixture of hydrogen (H2) & Nitrogen (N2) where the ratio of H2 to N2 should be 3:1 besides these two compounds the mixture will contain chart gases to be a limited degree, such as organ (Ar) & methane (CH4). For the ammonia plant at Vijaipur the source of H2 in water & hydrocarbon in the form of Natural Gas. The source of N2 is an in all ammonia plants the atmospheric air. The process steps which are necessary for producing ammonia from the above mentioned raw materials are as follows :a) Hydrocarbon feed in completely desulphurized in the desulphurization section. If naphtha is used it is pre-reformed to methane, hydrogen & carbon-dioxide in an adiabatic pre-reformer. b) The desulphurized hydrocarbon is reformed with steam and air to raw synthesis gas. This gas contains mainly hydrogen & nitrogen and also carbon monoxide (CO) & carbon dioxide (CO2). The reforming takes place at about 30-35 kg/cm2. c) In the gas purification section, CO in first converted to CO2 and H2 with steam in order to increase the H2 yield. CO2 in then removed in the CO2 removal section and residual CO & CO2 in afterwards reacted with H2 in methanator to form CH4. d) In the ammonia synthesis section, the purified synthesis gas after compression to pressure about 220kg/cm2, in converted into NH3 (Ammonia) by Habers Process. e) Process condensate is treated in the process condensate stripper. f) For further purification, it is sent to CPU (condensate polishing unit) make de-mineralised water for steam generation.

44

45

Ammonia Production Process:(I.) Desulphurization & Pre-reforming Section :-

The desulphurization unit consists of hydrogenators and H2S absorbers. In the hydrogenators the sulphur containing compounds in the natural gas are hydrogenated to H2S in the presence of Hydrogen Gas. This H2S is absorbed in one the two Zinc Oxide absorption vessels, which are operating in series and the sulphur level is reduced to approx. 0.05 ppm `S by weight. Reactions:R-SH + H2 R1SSR2 + 3H2 R1SR2 + 2H2 COS + H2 C4H4S + 4H2 RH + H2S R1H + R2H + 2H2S R1H + R2H + H2S CO + H2S C4H10 + H2S

Where `R is a radical of hydrocarbon.

(II.)

Hydrogenation :-

The natural gas passing to the process is preheated to 380-400 degree Celsius in the waste heat section of the primary reformer before entering the hydrogenation vessel. Hydrogen required for hydrogenation is being supplied as synthesis gas from the synthesis gas compressor and is added to the natural gas down-stream the preheated in the waste heat section. (The HDS reactor has one bed, 1.85 m high, containing 9m3 of Ni-Mo catalyst).

46

(III.)

Absorption:-

The ZnO absorber R 3202, A&B contains 30m3 of catalyst (Zinc oxide). Each vessel contains one bed with a bed highest of 3.60 m each. The normal operating temperature will be 350-400 degree Celsius but also at low temperatures the catalyst will react with hydrogen sulphide according to the following reaction:-

ZnO + H2S

ZnS + H2O

At normal operating temperature, the catalyst will also react with carbonyl sulphide.

ZnO + CoS

ZnS + CO2

To some extent, it will also remove organic sulphur compounds, however those should normally be prehydrogenated.

(IV.)

Reforming Section :-

In the reforming section, a gas containing synthesis gas in produced by catalytic reforming of a mixture of hydrocarbons and steam and addition of atmospheric air to adjust the hydrogen to nitrogen ratio.

Steam reforming of hydrocarbons can be described by the following endothermic reactions:47

1) CnH2n+2+ 2H2O 2) CH4 + 2H2 3) CO2 + H2

Cn-1 H2n + CO2 + 3H2 CO2 + 4H2 CO + H2O Heat

Heat

Heat (Reverse Shift)

The reforming reactions take place in two steps; in the primary reformer and in the secondary reformer.

The necessary heat of reaction in these two reforming steps in supplied in quite different ways. In the primary reformer the heat is supplied as indirect heat by firing. In the secondary reformer, the heat is supplied as direct combustion heat by mixing `air into gas. This burning gas mixture provides the heat input for the rest of the reforming reaction. The degree of reforming taking place in the primary reformer is so adjusted that the air supplied in the secondary reformer results in the required hydrogen/Nitrogen ratio of 3:1 in the ammonia synthesis gas.

The hydrocarbon steam mixture, which is preheated to 470-500 degree Celsius, passes downwards through vertical tubes filled with Ni-catalyst as well as heated extremely to a temperature of 800 C, to reform the hydrocarbons into CO, CO2 and H2. This partially reformed gas mixture is then passed on to the secondary reformer where `air is added in stoichiometric proportion to supply the required N2 (Nitrogen) as well as to facilitate the complete reforming and the methane concentration is about 0.30% on dry basis. The reformed gas passed through waste heat boiler to recover the heat by producing high pressure steam. The gas is further cooled in a steam super heater. The gas leaving the reforming section may have the following composition expressed in %volume on dry basis.

48

Hydrogen (H2) Carbon Monoxide (CO) Carbon dioxide (CO2) Nitrogen (N2) Argon (Ar) Methane (CH4)

55.6 56.4 mol % 13.0 13.8 mol % 7.3 8.7 mol % 22.3 22.7 mol % 0.3 mol % 0.3 mol %

(V.)

Shift Conversion :-

The high medium and low temperature shift converters are called gas purification section of the plant where the CO is converted into CO2.

Reaction in CO shift conversion:CO + H2O CO2 + H2.. (Exothermic) The reacted gas contains only 0.30% CO. The reacted part of the CO increases the H2 yield with simultaneous formation of CO2, which is more easily removable. The performance of the CO conversion section is strongly affecting the overall plant energy efficiency, as unconverted CO will consume H2 and form CH4 in the methanator, reducing the feed stock and increasing the inert gas level in the synthesis loop after cooling of a gas and condensation of most of the water content, the CO2 is removed in Benfield section of Line-I plant (ammonia) & GV section of Line-II plant (ammonia)

(VI.)

Removal of CO2 :-

A) Benfield process:This process is based on the use of 30% hot K2CO3 activated by DEA as absorbed. B) GV (Giammarco Vetrocole)process:This process is based on the use of 30% hot K2CO3 activated by DEA and Glycine vanadium pentaoxide & secondary amine as absorbent.

49

Reaction in CO2 removal: K2CO3 + CO2 + H2O 2 KHCO3

(VII.)

Methanation :-

After the CO2 removal the gas still contains small quantities of CO and CO2, which are poisonous to the ammonia catalyst. The CO & CO2 are therefore converted into methane in methanator.

Reactions :CO + 3H2 CH4 + H2O + Heat CO2 + 4H2 CH4 + H2O + Heat

(CO + CO2 content is normally reduced to <5 ppm)

(VIII.)

Ammonia Synthesis Section :-

Chemistry involved The ammonia synthesis takes place in the ammonia synthesis converter according to the following reaction: 3H2 + N2 2 NH3 + Heat i.e., 3 volume of hydrogen + 1 volume of nitrogen act to give 2 volume of ammonia.

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Steps:A) Methaned gas mixture is compressed in syn. Gas compressor to a pressure of 210 220 kg/cm2g. B) The reaction temperature in the catalyst bed in 360 525 C which is close to optimum level. C) The catalyst is a promoted iron catalyst containing small amount of nonreducible oxides. D) Ammonia synthesis 100Pa compression. E) Waste heat recovery by generation of high pressure steam and preheat of boiler fixed water (BFW). F) Gas-Gas heat exchanger for preheat of the converter feed gas. G) Water cooler in which a significant part of the product ammonia in condensate. H) Ammonia chillers, at different pressure levels, for further condensation of the product ammonia. I) Gas heat exchangers for recovery of the refrigeration energy. J) Product ammonia separator & start up heater (electric). The ammonia formed in refrigerated at 33 C and stores in the atmospheric tanks. The waste heat generated in various stages of exothermic reactions in utilized to produce steam at 105 ata pressure. This steam coupled with that from an auxiliary boiler provides power for all the devices in ammonia plant and satisfies the process steam requirement, reliability & energy efficiency. In ammonia plant Line-II the process air compressor used in Natural Gas turbine drive & exhaust of gas turbine and additional firing in heat recovery units (HRU) are used to produce HP steam at 117 MT/hr. The ammonia concentration at converter inlet is dependent on the cooling level in refrigeration chillers and the operating pressure. 5.6% NH3 at converter inlet correspond to 12 degree Celsius at a pressure of 209 kg/cm2g in the ammonia separately.
51

UREA TECHNOLOGY DEVELOPMENT AND LATEST STATUS

Urea or carbamide is an organic compound with the chemical formula CO(NH2)2. The molecule has two -NH2 groups joined by a carbonyl (C=O) functional group. Urea serves an important role in the metabolism of nitrogen-containing compounds by animals and is the main nitrogen-containing substance in the urine of mammals. It is solid, colourless, and odourless (although the ammonia that it gives off in the presence of water, including water vapour in the air, has a strong odour). It is highly soluble in water and non-toxic. Dissolved in water, it is neither acidic nor alkaline. The body uses it in many processes, the most notable one being nitrogen excretion. Urea is widely used in fertilizers as a convenient source of nitrogen. Urea is also an important raw material for the chemical industry. The synthesis of this organic compound by Friedrich Whler in 1828 from an inorganic precursor was an important milestone in the development of organic chemistry, as it showed for the first time that a molecule found in living organisms could be synthesized in the lab without biological starting materials (thus contradicting a theory widely prevalent at one time, called vitalism). Urea was first prepared synthetically in 1828 from Ammonia & Cyaunric Acid (HCNO): NH3 + HCNO NH2CONH2

The present method of synthesizing Urea from Ammonia & CO2 has been known since 1868 but the commercial production by this method started only in 1922 in Germany. Since then, this has been the most popular method of producing Urea. More than 90% of world production of urea is destined for use as a nitrogenrelease fertilizer. Urea has the highest nitrogen content of all solid nitrogenous fertilizers in common use. Therefore, it has the lowest transportation costs per unit of nitrogen nutrient. The standard crop-nutrient rating of urea is 46-00.{ICIS, http://www.icis.com/v2/chemicals/9076559/urea/uses.html}

52

Many soil bacteria possess the enzyme urease, which catalyzes the conversion of the urea molecule to two ammonia molecules and one carbon dioxide molecule, thus urea fertilizers are very rapidly transformed to the ammonium form in soils. Among soil bacteria known to carry urease, some ammoniaoxidizing bacteria (AOB) such as species of Nitrosomonas are also able to assimilate the carbon dioxide released by the reaction to make biomass via the Calvin Cycle, and harvest energy by oxidizing ammonia (the other product of urease) to nitrite, a process termed nitrification.[8] Nitrite-oxidizing bacteria, especially Nitrobacter, oxidize nitrite to nitrate, which is extremely mobile in soils and is a major cause of water pollution from agriculture. Ammonia and nitrate are readily absorbed by plants, and are the dominant sources of nitrogen for plant growth. Urea is also used in many multi-component solid fertilizer formulations. Urea is highly soluble in water and is, therefore, also very suitable for use in fertilizer solutions (in combination with ammonium nitrate: UAN), e.g., in 'foliar feed' fertilizers. For fertilizer use, granules are preferred over prills because of their narrower particle size distribution, which is an advantage for mechanical application. MANUFACTURING PRINCIPLES: The urea is produced by direct synthesis of liquid Ammonia & Carbon di-oxide gas by following reactions. 2 NH3 + CO2 NH2 COO NH4 NH2COO NH4 Ammonium Carbamate + 37.64 Kcal/Mole -- (i)

NH2 CONH2 + H2O - 6.32 Kcal/Mole -- (ii) Urea

The formation of Ammonium Carbamate through reaction (i) is instantaneous and completes very fast. It is highly exothermic in nature. Reaction no. (ii) for Urea formation is, however, rather slow and little bit endothermic. An ideal process at 1 ata and 25C will, therefore, yield a net heat of 31.32 Kcal/Mole. In actual practice the Urea Production process is energy consuming due to the following reasons. a) b) c) d) e) Heat is lost in evaporation of liq. NH3 & water formed in reaction. Keeping the Urea formed in molten stage. Synthesis is done on high pr. &temperature for better conversion. Heat is added to decompose unconverted Carbamate Power is required to feed back the separated CO2 and NH3 to the reactor pressure.
53

The formation of urea is represented by (ii) reaction which proceeds towards equilibrium state and is governed by the operating pressure and temperature of synthesis mixture, mole ratio of NH3/CO2 and H2O/CO2 and residence time.

FACTORS EFFECTING UREA PROCESS: Effect of Temperature: Reaction (i) is exothermic and therefore, low temperature favors forward reaction. Reaction (ii) is endothermic and favored at high temperature. To get sufficient conversion, an optimum temperature is selected. It is observed that maximum equilibrium conversion occurs at 190 200C. Effect of Pressure: There is reduction in volume in the overall reaction and so high pressure favors the forward reaction. Reactor pressure is selected according to temperature so that it remains higher than the dissociation pressure of Carbamate to avoid reversal of (i) reaction. Effect of Concentration of reactants: Increase in NH3 or CO2 concentration should theoretically increase the percentage conversion in the Reactor. However, in actual practice it has been observed that excess CO2 does not help much but excess NH3 greatly enhances the CO2 conversion. Presence of water shifts the (ii) reaction in reverse direction. Hence lesser H2O/CO2 ratio favors urea formation. However, water has to be maintained in system to help recycling unconverted CO2& NH3 back to reactor & maintaining the temperature in reactor. Higher Residence Time: The reaction to form urea approaches to chemical equilibrium & the reaction rate decreases with time. It can only be increased with the increase in residence time. Higher residence time can also compensate other unfavorable conditions. The outlet product from the urea reactor consists of Urea, unconverted Carbamate, excess NH3 and water. This mixture is processed further to recover and recycle back the unconverted reactants. The various processes available so far differ principally in the manner in which these unconverted reactants are recovered and recycled back to the Reactor or otherwise, processed further in other plants for producing different type of fertilizers. The second reaction (ii) of urea formation indicates that volume increases in forward direction and therefore, favored at low pressure. Also this reaction is
54

endothermic and thus reaction rate increases with increase in temperature to increase urea conversion. It is, therefore, obvious that recovery of unconverted Carbamate shall be achieved by decomposition by reducing pressure and adding heat.

Fig1. BASIC PROCESS FLOW DIAGRAM OF NFL UREA PLANT

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EVOLVEMENT OF UREA TECHNOLOGY: The mode of utilization of the recovered NH3& CO2 made the basic difference between all the available process setups. In fact, the method of recovering unconverted Ammonia & CO2 had come a long way since very earliest plants established to manufacture urea and thereby increasing efficient utilization of raw materials and minimizing consumption of energy. Initially, the urea plants were operated on 'Once Through' principle. The low pressure Ammonia and carbon di-oxide from the decomposition stage were not recycled back to the reactor due to the cost involved in recompressing them. Rather, the gases recovered were used to produce some other type of fertilizer in associated facilities. In some of the processes, the ammonia recovered during Carbamate decomposition stage used to be condensed & recycled back to the reactor. The leftover CO2 used to be separated out and vented. This system of recovery was called 'Partial Recycle Process'. These types of plants were outdated since long due to draw backs of higher utility consumption, lower conversion efficiency and higher energy consumption. Thereafter, all the plants were based on 'Total Recycle Process' is which the reactor effluent used to be decomposed in a series of decomposers operating at very low pressure as compared to reactor. The recovered vapours were condensed in the form of Carbamate solution and recycled back to the reactor. Though this type of arrangement was very efficient in terms of raw material, the consumption of energy was considerably high because of steam consumption for decomposition and the lower potential of heat recovery due to low pressure levels in decomposition stages. The pumping of recovered Carbamate solution had also been a contributing factor to the higher energy consumption. In 1970s, M/s Stami Carbon and M/s Snamprogetti, developed 'Stripping Process' which was a much better way of total recycling of the Carbamate with a substantial improvement in energy consumption levels. In these processes, the dissociation of ammonium Carbamate was, first, performed at the reactor pressure rather than setting down the pressure. This was done with the help of a stripping media by shifting partial pressure of one of the component. The use of CO2 by Stami Carbon and NH3 by Snamprogetti as stripping media has revolutionized the Urea Industry. Most of the licensers are using this technique now-a-days to produce urea in an efficient manner. The way of heat recovery is, however, different from process to process.
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STRIPPING PROCESS: The stripping concept is based on the application of the Law of Mass Action to the Carbamate formation / decomposition equilibrium. If the concentration of one of the component in reactor effluent solution is artificially lowered, the ammonium Carbamate will decompose until the correct equilibrium is restored. This is done by passing the reactor effluent through a steam heated stripper working at same pressure level as of reactor, which is injected with one of the gaseous feeds. This has the effect of raising the partial pressure of the component used as the stripping gas, which reduces the partial pressure of the other gas and help in decomposing of Carbamate. As per Henry's law, the partial pressure of a component in vapour mixture is proportional to the concentration of that component in the solution at system pressure. Pa ~ Ca If the partial pressure of any of the component i.e. NH3& CO2 in stripper is raised artificially by adding any of the component, the partial pressure of the other component reduces and correspondingly, the concentration of that component in solution reduces by decomposition of Carbamate. This causes decomposition of Carbamate solution. The heat for decomposition is supplied from outside. This heat is at a higher level but requirement is less because decomposition is assisted by stripping effect. The heat of condensation of the evolved gases is sufficient enough to recover it by producing low pressure steam instead of wasting to cooling water. As the stripper & Carbamate condenser operates at reactor pressure, no pump is required to recycle the condensed Carbamate solution back to the reactor. It results in establishment of an internal recycle of both ammonia and CO2 in urea reactor system to the maximum extent. The left over Carbamate is passed on to the downstream section for recovery which is very less in quantity and thus requires low energy for decomposition. The operating pressure of the synthesis loop has also been brought down which means direct saving in power for feed and pumping back the recovered Carbamate.

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SALIENT FEATURES OF VARIOUS UREA MANUFACTURING PROCESSES: Apart from increase in CO2 conversion in reactor, urea production technology has been advanced in other fields also over a period of time. Temperature profile, residence time and mole ratio of NH3 : CO2 has been optimized in such a manner that CO2 conversion is maximized but not at the expense of energy consumption. The system of heat recovery within the plant battery limit has also been improved upon. Beside process parameters, the production cost of urea has also been brought down by increasing the plant size upto a level of more than 2000 TPD in single stream. The use of conventional total recycle processes is almost negligible in new plants due to consumption of high energy. All the licensers supplying urea production technology adopts the route of stripping process in one form or other. The basic difference being the stripping media, set up of synthesis section equipment for internal recycle of Carbamate and heat recovery arrangements in the downstream section of the plant. Some of the latest processes available now a days are outlined below. (1) SNAM PROGETTI'S NH3 STRIPPING PROCESS:

This process is based on stripping of reactor outlet solution by NH3. Reactor is fed with the excess ammonia which acts as the stripping media in the Stripper. Reactor is operated at a pressure of 160 ata and at a temperature of 188-190C keeping a NH3/CO2 ratio of 3.6. Mixing trays are provided in the reactor to enhance the conversion in the reactor. About 65% of CO2 is converted to urea in the reactor per pass. The reactor effluent is sent to falling film stripper working at a pressure of 146 ata. Excess ammonia present in the reactor solution is used as the stripping media. Heat for stripping is supplied by 25 ata steam. The stripped off gas is condensed in the Carbamate condenser alongwith recycle Carbamate from downstream plant and sent to reactor via an ejector using HP ammonia feed as the driving media. Low pressure steam is generated in HP Carbamate condenser and used in LP section / vacuum section concentrators. Recovery of unconverted solution is carried out in two stages of 15 ata & 3.5 ata and finally concentrated in two stage vacuum sections before prilling.

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(2)

STAMI CARBON'S CO2 STRIPPING PROCESS:

This process is based on the stripping process using carbon di oxide gas as the stripping media. This process was developed in 1960. The process has greatly been improved since its inception. In original process synthesis took place at 140 ata pressure and 180-185C. A mole ratio of NH3& CO2 is maintained at around 2.9. About 58% of CO2 is converted to urea in the reactor per pass. More than 80% of the unconverted NH3& CO2 is recovered in the stripper itself where CO2 is fed as stripping media. Medium pressure decomposition stage is also eliminated as the process does not contain excess ammonia. Heat of Carbamate condensation is recovered in the form of Low Pressure Steam. Urea solution from the stripper is directly letdown to 3-6 Kg./Cm2 and recovered Carbamate vapours are recycled back to H.P. Stripper after condensation. Urea solution from LP section is concentrated in two stage vacuum system & then prilled.

(3)

ACES PROCESS(Advanced Process for Cost & Energy Saving):-

This process of Toyo Engineering combines a total recycle process with stripping process using CO2 feed as stripping agent. Reactor operates at 176 Kg./Cm2 pressure and ata temperature of 190C with mole ratio of NH3 /CO2 of 4.00. About 68% of the CO2 is converted to urea in reactor per pass. More than 65% of unconverted Carbamate is stripped off in the stripper. Stripped off gases are recycled back to the reactor after condensation in high pressure condensers no. 1 & 2 . LP steam is generated in one of the condenser whereas the second condenser is utilized for decomposition in the MP section. In addition, the MP section condensation heat is further utilized in evaporation section. This has brought down the energy consumption in ACES plant to a low level. (4) IDR PROCESS: (Isobaric Double Recycle):-

This process of Montedison is an economical process of production of urea by using two strippers working in series with NH3 and CO2 as stripping agent in each stripper. The reactor is divided in two parts by partition plate along-with mixing trays. Synthesis takes place at 200 ata pressure and at temperature of 185 - 190C. A ratio of NH3/CO2 equal to 4.25 is maintained in the reactor which helps in converting 70% of the CO2 in urea per pass. NH3 feed in divided into two parts i.e. one part going to NH3 stripper & other one to the reactor to maintain the temperature profile in reactor. CO2 feed is directly sent to second
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stripper. The unconverted stripped off gases from 1st stripper are sent to upper portion of reactor & from 2nd stripper to Carbamate condenser. The condensed Carbamate is recycled to the reactor along-with Carbamate solution from the downstream recovery sections. Steam of 7 ata rating is generated in the Carbamate condenser which is utilized in the recovery section.

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VARIOUS EQUIPMENTS AVAILABLE FOR QUALITY CONTROL and LAB TESTING AT CENTRAL LAB, NFL VIJAIPUR: 1. SPECTROPHOTOMETER (UV mini 1240):A spectrophotometer is a photometer (a device for measuring light intensity) that can measure intensity as a function of the light source wavelength.

Design
There are two major classes of devices: single beam and double beam. A double beam spectrophotometer compares the light intensity between two light paths, one path containing a reference sample and the other the test sample.

A single beam spectrophotometer measures the relative light intensity of the beam before and after a test sample is inserted. Although comparison measurements from double beam instruments are easier and more stable, single beam instruments can have a larger dynamic range and are optically simpler and more compact.

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Historically, spectrophotometers use a monochromator containing a diffraction grating to produce the analytical spectrum. The grating can either be movable or fixed. If a single detector, such as a photomultiplier tube or photodiode is used, the grating can be scanned stepwise so that the detector can measure the light intensity at each wavelength (which will correspond to each "step"). Arrays of detectors, such as charge coupled devices (CCD) or photo diode arrays (PDA) can also be used. In such systems, the grating is fixed and the intensity of each wavelength of light is measured by a different detector in the array. UV-visible spectrophotometry The most common spectrophotometers are used in the UV and visible regions of the spectrum, and some of these instruments also operate into the near-infrared region as well. Visible region 400700 nm spectrophotometry is used extensively in colorimetry science. Ink manufacturers, printing companies, textiles vendors, and many more, need the data provided through colorimetry. Scientists use this instrument to measure the amount of compounds in a sample. If the compound is more concentrated more light will be absorbed by the sample; within small ranges, the Beer-Lambert law holds and the absorbance between samples vary with concentration linearly.

Fig. UV mini 1240 spectrophotometer

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2. Photoelectric flame photometer: A photoelectric flame photometer is a device used in inorganic chemical analysis to determine the concentration of certain metal ions, among them sodium, potassium, lithium, and calcium. It should be noted that Group 1 and Group 2 metals are quite sensitive to Flame Photometry due to their low excitation energies. In principle, it is a controlled flame test with the intensity of the flame colour quantified by photoelectric circuitry. The intensity of the colour will depend on the energy that had been absorbed by the atoms that was sufficient to vaporise them. The sample is introduced to the flame at a constant rate. Filters select which colours the photometer detects and exclude the influence of other ions. Before use, the device requires calibration with a series of standard solutions of the ion to be tested. Flame photometry is crude but cheap compared to flame emission spectroscopy, where the emitted light is analysed with a monochromator. Its status is similar to that of the colorimeter (which uses filters) compared to the spectrophotometer (which uses a monochromator). It also has the range of metals that could be analysed and the limit of detection is also considered.

Fig. Flame Photometer.

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3. pH meter (ESICO Model-1012)

A pH meter is an electronic instrument used for measuring the pH (acidity or alkalinity) of a liquid (though special probes are sometimes used to measure the pH of semi-solid substances). A typical pH meter consists of a special measuring probe (a glass electrode) connected to an electronic meter that measures and displays the pH reading. 3.1. The probe

The pH probe measures pH as the activity of hydrogen cations surrounding a thin-walled glass bulb at its tip. The probe produces a small voltage (about 0.06 volt per pH unit) that is measured and displayed as pH units by the meter.

3.2.

The meter

The meter circuit is no more than a voltmeter that displays measurements in pH units instead of volts. The input impedance of the meter must be very high because of the high resistance approximately 20 to 1000 M of the glass electrode probes typically used with pH meters. The circuit of a simple pH meter usually consists of operational amplifiers in an inverting configuration, with a total voltage gain of about 17. The inverting amplifier converts the small voltage produced by the probe (+0.059 volt/pH) into pH units, which are then offset by seven volts to give a reading on the pH scale. For example:

At neutral pH (pH 7) the voltage at the probe's output is 0 volts. 0 * 17 + 7 = 7. At basic pH, the voltage at the probe's output ranges from +0 to +0.41 volts (7 * 0.059 = 0.41). So for a sample of pH 10 (3 pH units above neutral), 3 * 0.059 = 0.18 volts), the output of the meter's amplifier is 0.18 * 17 + 7 = 10. At acid pH, the voltage at the probe's output ranges from 0.41 volts to 0. So for a sample of pH 4 (3 pH units below neutral), 3 * 0.059 = 0.18 volts, the output of the meter's amplifier is 0.18 * 17 + 7 = 3.94.

The two basic adjustments performed at calibration (see below) set the gain and offset of the inverting amplifier. 3.3. Calibration and use

For very precise work the pH meter should be calibrated before each measurement. For normal use calibration should be performed at the beginning
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of each day. The reason for this is that the glass electrode does not give a reproducible e.m.f. over longer periods of time. Calibration should be performed with at least two standard buffer solutions that span the range of pH values to be measured. For general purposes buffers at pH 4 and pH 10 are acceptable. The pH meter has one control (calibrate) to set the meter reading equal to the value of the first standard buffer and a second control (slope) which is used to adjust the meter reading to the value of the second buffer. A third control allows the temperature to be set. Standard buffer sachets, which can be obtained from a variety of suppliers, usually state how the buffer value changes with temperature. For more precise measurements, a three buffer solution calibration is preferred. As pH 7 is essentially, a "zero point" calibration (akin to zeroing or taring a scale or balance), calibrating at pH 7 first, calibrating at the pH closest to the point of interest ( e.g. either 4 or 10) second and checking the third point will provide a more linear accuracy to what is essentially a non-linear problem. Some meters will allow a three point calibration and that is the preferred scheme for the most accurate work. Higher quality meters will have a provision to account for temperature coefficient correction, and high-end pH probes have temperature probes built in. The calibration process correlates the voltage produced by the probe (approximately 0.06 volts per pH unit) with the pH scale. After each single measurement, the probe is rinsed with distilled water or deionized water to remove any traces of the solution being measured, blotted with a scientific wipe to absorb any remaining water which could dilute the sample and thus alter the reading, and then quickly immersed in another solution. 3.4. Storage conditions of the glass probes

When not in use, the glass probe tip must be kept wet at all times to avoid the pH sensing membrane dehydration and the subsequent dysfunction of the electrode. A glass electrode alone (i.e., without combined reference electrode) is typically stored immersed in an acidic solution of around pH 3.0. In an emergency, acidified tap water can be used, but distilled or deionised water must never be used for longer-term probe storage as the relatively ionless water "sucks" ions out of the probe membrane through diffusion, which degrades it. Combined electrodes (glass membrane + reference electrode) are better stored immersed in the bridge electrolyte (often KCl 3 M) to avoid the diffusion of the electrolyte (KCl) out of the liquid junction.
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Fig. pH meter

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4. Electrical conductivity meter (Model 341E):An electrical conductivity meter (EC meter) measures the electrical conductivity in a solution. Principle of operation The common laboratory conductivity meters employ a potentiometric method and four electrodes. Often, the electrodes are cylindrical and arranged concentrically. The electrodes are usually made of platinum metal. An alternating current is applied to the outer pair of the electrodes. The potential between the inner pair is measured. Conductivity could in principle be determined using the distance between the electrodes and their surface area using the Ohm's law but generally, for accuracy, a calibration is employed using electrolytes of well-known conductivity.

Fig. Electrical Conductivity meter working diagram.

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5. Nephelo Turbidity meter (Systronics Model 306):A nephelometer is a stationary or portable instrument for measuring suspended particulates in a liquid or gas colloid. A nephelometer measures suspended particulates by employing a light beam (source beam) and a light detector set to one side (often 90) of the source beam. Particle density is then a function of the light reflected into the detector from the particles. On the other hand a turbidity meter measures the intensity of light emerging out of the solution or the amount of light left unscattered by the suspended particles. The units of turbidity from a calibrated nephelometer are called Nephelometric Turbidity Units (NTU).

Fig. Nephelo-Turbidity meter.

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6. Mitsubishi Moisture meter (CA 200):The moisture meter utilises Karl Fischer Coulometric titration to determine trace amounts (g/L) of water (moisture) in an oil sample. Principle The main compartment of the titration cell contains the anode solution plus the analyte. The anode solution consists of an alcohol (ROH), a base (B), SO2 and I2. A typical alcohol that may be used is methanol or diethylene glycol monoethyl ether, and a common base is imidazole. The titration cell also consists of a smaller compartment with a cathode immersed in the anode solution of the main compartment. The two compartments are separated by an ion-permeable membrane. The Pt anode generates I2 when current is provided through the electric circuit. The net reaction as shown below is oxidation of SO2 by I2. One mole of I2 is consumed for each mole of H2O. In other words, 2 moles of electrons are consumed per mole of water. BI2 + BSO2 + B + H2O 2BH+I + BSO3 BSO3 + ROH BH+ROSO3 The end point is detected most commonly by a bipotentiometric method. A second pair of Pt electrodes is immersed in the anode solution. The detector circuit maintains a constant current between the two detector electrodes during titration. Prior to the equivalence point, the solution contains I- but little I2. At the equivalence point, excess I2 appears and an abrupt voltage drop marks the end point. The amount of current needed to generate I2 and reach the end point can then be used to calculate the amount of water in the original sample. The moisture meter can detect even trace quantities of water (in parts per billion) which is present in any oil sample. This is necessary as the oil is used for lubrication at high temperature and rpm of rotating parts. Even minute quantities of moisture can bubble up in such conditions and can cause mechanical failure.

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Fig. Diagram of a Moisture meter.

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7. Viscometer:A viscometer (also called viscosimeter) is an instrument used to measure the viscosity of a fluid. For liquids with viscosities which vary with flow conditions, an instrument called a rheometer is used. Viscometers only measure less than one flow condition. The drag caused by relative motion of the fluid and a surface is a measure of the viscosity. The CGS unit of viscosity is Poise (P) and Poise per density at the same temperature is Stokes (St). SI unit of viscosity is Pascal seconds (Pa-s). 1 Pa-s = 10 P.

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8. Gas Chromatograph (Shimadzu GC-14B) :Gas chromatography (GC), is a common type of chromatography used in analytical chemistry for separating and analysing compounds that can be vaporized without decomposition. Typical uses of GC include testing the purity of a particular substance, or separating the different components of a mixture (the relative amounts of such components can also be determined). In gas chromatography, the mobile phase (or "moving phase") is a carrier gas, usually an inert gas such as helium or an unreactive gas such as nitrogen. The stationary phase is a microscopic layer of liquid or polymer on an inert solid support, inside a piece of glass or metal tubing called a column. The gaseous compounds being analysed interact with the walls of the column, which is coated with different stationary phases. This causes each compound to elute at a different time, known as the retention time of the compound. The comparison of retention times is what gives GC its analytical usefulness.

Fig. Diagram of a Gas Chromatograph In NFL Vijaipur, for the analysis of natural gas we use Standard Operating Procedure (SOP) defined by ASTM D1945 standards. According to which the optimum conditions for analysis of Natural Gas are:1. Carrier Pressure: Column I = 1kg/cm2 Column II = 1 kg/cm2

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2. Column Material = PORAPACK-N 3. Pre-column drying agent = DRIERITE 4. Column temperature = 90 degrees Celsius 5. Injection temperature = 100 degree Celsius 6. Detector = TCD (Thermal Conductivity Detector) 7. Detector temperature = 150 degree Celsius 8. Bridge current = 100mA 9. Polarity = 1 10. Sample loop = 3 11. Column selection = 1

Composition of NG obtained as on 26/06/2013:Sr. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. CONSTITUENT N2 CH4 CO2 C-2 C-3 I-C4 n-C4 I-C5 n-C5 C-6 and above % COMPOSITION 0.2087 90.1639 4.119 4.7494 0.7461 0.003 0.0008 0.0092 -

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9. Ion Chromatograph (Model ICS-900) :Principle Ion-exchange chromatography retains analyte molecules on the column based on coulombic (ionic) interactions. The stationary phase surface displays ionic functional groups (R-X) that interact with analyte ions of opposite charge. This type of chromatography is further subdivided into cation exchange chromatography and anion exchange chromatography. The ionic compound consisting of the cationic species M+ and the anionic species B- can be retained by the stationary phase. Cation exchange chromatography retains positively charged cations because the stationary phase displays a negatively charged functional group:
R-X-C+ + M+B- R-X-M+ + C+B-

Anion exchange chromatography retains anions using positively charged functional group:
R-X+A- + M+B- R-X+B- + A-M+

Note that the ion strength of either C+ or A- in the mobile phase can be adjusted to shift the equilibrium position and thus retention time. The ion chromatogram shows a typical chromatogram obtained with an anion exchange column. Typical technique A sample is introduced, either manually or with an auto-sampler, into a sample loop of known volume. A buffered aqueous solution known as the mobile phase carries the sample from the loop onto a column that contains some form of stationary phase material. This is typically a resin or gel matrix consisting of agarose or cellulose beads with covalently bonded charged functional groups. The target analytes (anions or cations) are retained on the stationary phase but can be eluted by increasing the concentration of a similarly charged species that will displace the analyte ions from the stationary phase. For example, in cation exchange chromatography, the positively charged analyte could be displaced by the addition of positively charged sodium ions. The analytes of interest must then be detected by some means, typically by conductivity or UV/Visible light absorbance.
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Fig. Working diagram of an ion chromatograph.

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VARIOUS WATER QUALITY CONTROL TESTS CARRIED OUT AT CENTRAL LAB, NATIONAL FERTILIZERS LTD. VIJAIPUR: 1. pH :pH affects most of the chemical reactions which take place in water and wastewater treatment plants, so it is important to test pH of the source and treated water frequently. Changes in pH of the source water may require the operator to change the feed rate of various chemicals. In contrast, changes in pH of the treated water may indicate that chemicals are not being fed properly, perhaps due to a chemical feeder running out of chemicals. The pH test explained in this lab exercise gives the knowledgeable operator one of the best indicators of the chemical balance of the plant's water. pH is typically measured using a pH meter, so this is one of the simplest tests performed in the water and wastewater laboratory. Basically, measuring pH consists of calibrating the instrument, placing the electrodes in a well-mixed sample, and then reading the pH directly from the pH meter. 2. Conductivity :Electrical conductivity or specific conductance is the reciprocal quantity, and measures a material's ability to conduct an electric current. It is commonly represented by the Greek letter (sigma), but (esp. in electrical engineering) or are also occasionally used. Its SI unit is Siemens per meter (Sm1)

3. Turbidity :Turbidity of water is caused by suspended particles, primarily of clay, silt, organic matter, and microorganisms. In natural waters, turbidity can range from a few NTU to about 1,500 NTU. While turbidity is not harmful by itself, excess turbidity hinders the efficiency of disinfection which can result in unsafe drinking water. As a result, the EPA Drinking Water Standards limit turbidity to 1 NTU in filtered water. In practice, coagulation, flocculation, and sedimentation followed by effective filtration should result in effluent water containing less than 0.2 NTU.

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In a nephelometer, light reflects off turbidity particles in the water and is measured by a photomultiplier tube. The amount of light reaching the photomultiplier tube is proportional to the amount of turbidity in the sample water. The test for turbidity is a physical test rather than a chemical test. An instrument called a nephelometer is used to measure the amount of light which is scattered by hitting turbidity particles in the water. In the treatment plant, operators usually test the turbidity of the finished water at intervals throughout the day. This gives the operator an indication of how well the water is being treated. If the effluent water has an unexpectedly high turbidity, then the chemical feed rates may need to be adjusted or the filters may need to be backwashed.

4. Free chlorine:Procedure Take 5mL Chlorotex reagent in a test tube. Add 50mL of sample water. Vigorously shake and observe the colour developed after 1 min. Sr. No. 1. 2. 3. 4. 5. Colour developed Milky Buff Pink Violet Navy blue
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Amount of free chlorine (in ppm) 0.1 0.2 0.5 0.6 1.0

5. Alkalinity :Alkalinity is a measure of the capacity of a solution to neutralize a strong acid. We can calculate the amount of alkalinity in water by titrating the sample water with an acid, using an indicator to determine when the sample water's pH has dropped to a certain level - the endpoint. Titration does not tell us the actual types of alkalinity present in the water. So we cannot report our results as ppm of carbonate, bicarbonate, etc. Instead, we report the amount of alkalinity as calcium carbonate equivalent, which is the amount of alkalinity in terms of its equivalent value of calcium carbonate. The pH of water determines what type(s) of alkalinity can be found in the water. By performing two different alkalinity tests with different endpoint pH values, we are able to estimate the proportions of carbonate, bicarbonate, and hydroxide alkalinity in the water. The two tests also help us determine whether the water is corrosive and whether it is caustic. Equipment

25 or 50 mL burette, graduated in 0.1 mL burette support 100 mL graduated cylinder rubber-tipped stirring rod, or magnetic stirrer and stir bar white porcelain evaporating dish, 4.5 inches in diameter

Reagents The reagents needed include the indicator and the acid used for the titration. The acid is N/50 sulphuric acid, which is the same as 0.02 N sulphuric acids. The indicator for the total alkalinity test will be:

Methyl orange indicator, in a 50 to 100 mL dropping bottle. Store the solution in a dark place.

Procedure 1. Clean the burette and fill almost to the top with N/50 sulphuric acid. Then run some acid to waste until the "zero" mark is reached. This should leave the stopcock and tip of the burette full of the solution.
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2. Measure out 100 mL of the water to be tested and pour into a clean white porcelain evaporating dish. 3. With a dropping bottle, add 2 or 3 drops of methyl orange or methyl purple indicator to the sample and stir. When alkalinity is present, the solution becomes yellow when methyl orange is added or becomes green when methyl purple is added. 4. Slowly and carefully add N/50 sulphuric acid from the burette to the contents of the dish until the faintest pink colouration appears that is, until the colour of the solution is no longer yellow. While adding the acid, the solution should be gently stirred with the stirring rod. It is often advantageous to set up two 100 mL samples, adding methyl orange to each and acid to only one while the other is held alongside so that the colours may be compared and the colour change to pink can be better recognized. 5. Calculate the total alkalinity, as follows: T. alkalinity = (mL of acid) (10 ppm/mL) Example: if 1.5 mL of acid were used in the titration, then the total alkalinity would be: T. alkalinity = (1.5) (10) = 15 ppm CaCO3

Given P=0 2P < M 2P = M 2P > M P=M

Hydroxide 0 0 0 2P - M M

Carbonate 0 2P 2P 2(P-M) 0

Bicarbonate M M - 2P 0 0 0

Fig. Table to determine alkalinity due to OH-, CO32- and HCO3-

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6. Total Hardness :-

The primary causes of hardness are calcium (Ca+2) and magnesium (Mg+2) ions, but other metals such as strontium, ferrous iron, manganous, aluminium, and ferric iron can also contribute to hardness. Equipment

beakers rubber-tipped stirring rod, or magnetic stirrer and stir bar 25 or 50 mL burette, graduated in 0.1 mL burette support

Reagents

distilled water Ammonium Chloride buffer solution Eriochrome Black-T indicator N/50 EDTA titrant

Procedure 1. Use a sample size of 100 mL. 2. Add 2 mL of buffer solution to the beaker (or more if you use a larger water sample.) This will change the pH of the sample water to about 10.0 to 10.1. Stir. 3. Add 1 to 2 drops of indicator solution to the beaker (or more if you use a larger water sample.) Stir. 4. Titrate with EDTA titrant, stirring at intervals, until the indicator changes colour. The colour will change from reddish to blue, although incandescent lights tend to give the final solution a reddish tinge. 5. Record the amount of EDTA titrant which was required to reach the endpoint. 6. Calculate and record the amount of hardness (as ppm CaCO3) in the water using the following formula: Total Hardness = (mL of titrant) X (molarity of titrant) X 100 (mL sample)

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7. Calcium Hardness :Equipment

beakers rubber-tipped stirring rod, or magnetic stirrer and stir bar 25 or 50 mL burette, graduated in 0.1 mL burette support

Reagents

distilled water Ammonium Chloride buffer solution Patton and Reeders or Muroxide indicator N/50 EDTA titrant

Procedure 1. Use a sample size of 100 mL. 2. Add 2 mL of NaOH buffer solution to the beaker. Stir. 3. Add 1 to 2 drops of indicator solution to the beaker (or more if you use a larger water sample.) Stir. 4. Titrate with N/50 EDTA titrant, stirring at intervals, until the indicator changes colour. The colour will change from violet to blue, although incandescent lights tend to give the final solution a reddish tinge. 5. Record the amount of EDTA titrant which was required to reach the endpoint. 6. Calculate and record the amount of hardness (as ppm CaCO3) in the water using the following formula: Ca Hardness = (mL of titrant) X (molarity of titrant) X 100 (mL sample) Mg hardness = Total Hardness Calcium Hardness.

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8. Test for determination of Silica :The first method of silica colorimetric analysis is called the Molybdosilicate method. In this method, the analyst dilutes the samples within the range for testing. The range for testing is dependent on what size cell is being used. 1. A volume of 50mL is used during the colour development in volumetric flask. 2. 1mL sample is treated with 2 milliliters of 1:1 HCl and two milliliters of ammonium molybdate reagent. The sample is then inverted and allowed to set for five minutes. 3. Two milliliters of oxalic acid and Metol Reagent are added and mixture was allowed to stand for 10 minutes to develop blue colour of silicomolybdate. The oxalic acid is used to remove any interference from phosphate and decrease interferences from tannin. 4. The sample is then run photometrically at 815nm in a 25mm cuvette.

Calculation:Amount of silica (in ppm) = 159 X Absorbance (mL sample) Example:Absorbance of PTP filter Water sample on 26/06/2013 = 0.088 .. Amount of silica = 159 X 0.088 = 13.992 ppm 1

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9. Test for the determination of Ortho Phosphate :(I) In cooling water sample at Central lab. (II) In blow-down water sample at DMW plant. (I) Reagents

DM water for make-up N/4 H2SO4 solution. Ammonium Molybdate Ascorbic acid

Procedure 1. A sample of 5-7 mL was taken in a volumetric flask. 2. Add 2 mL of N/4 H2SO4 solution to the flask. 3. Add 2mL of Ammonium Molybdate solution, so that yellow colour appears. 4. Add 1mL of ascorbic acid and let the solution stand for 1 minute. 5. Make-up the volume to 25mL by adding DM water. 6. The sample was then analysed in spectrophotometer at 700nm wavelength in a 10mm cuvette. Calculation Amount of PO43-= 150 X absorbance (mL sample) (II) Here the phosphate ion is tested in blow-down water from the boiler where it is found as a result of adding TSP (Na3PO4) in the boiler to prevent scaling. Reagents

DM water for make-up Hydraquinone.

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Ammonium Molybdate K2CO3buffer solution

Procedure 1. A sample of 10 mL was taken from the blow-down water in a volumetric flask. 2. Add5 mL of Ammonium Molybdate solution to the flask. 3. Stand for 5 minutes. 4. Add 1mL of Hydraquinone and 2mL K2CO3buffer and let the solution stand for 10 minutes. 5. Make-up the volume to 100mL by adding DM water. 6. The sample was then analysed in spectrophotometer at 650nm wavelength in a 10mm cuvette. Calculation Amount of PO43-(in ppm) = 1.515 X absorbance X 1000 (mL sample) Example: - The observed absorbance was found to be 0.178. .. Amount of PO43- = 1.515 X 0.178 X 1000 10 = 2.7 ppm in blow-down water.

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10.Test for determination of Iron content in water from cooling tower:Iron can enter water in the distribution system when iron-containing pipes are corroded. In either case, iron in water will cause customer complaints due to its red color and its tendency to stain plumbing fixtures and laundry. As a result, the recommended limit for iron in water is 3 ppm. Equipment

125 mL erlenmeyer flasks. (Erlenmeyer flasks are used for general mixing and measuring.) 100 mL and 1,000 mL volumetric flasks. Various beakers, graduated cylinders, and pipets. Bunsen burner.

Reagents

1:1 Hydrochloric acid. Hydroxylamine solution. Ammonium acetate buffer solution. Phenanthroline solution.

Procedure 1. Mix the sample well. Using a graduated cylinder, measure out 50.0 mL into a 125 mL erlenmeyer flask. 2. Add 2 mL of concentrated hydrochloric acid to the sample. 3. Boil until the volume of the sample is reduced to 15 to 20mL. 4. Add 5 mL of hydroxylamine solution as soon as the beaker is taken off hot-plate. 5. Cool the sample to room temperature and transfer it to a 100 mL volumetric flask. 6. Add 10mL of ammonium acetate buffer solution. 7. Add 2mL of phenanthroline solution. 8. Volume was made upto 50mL using DM water. 9. The sample was then analyzed in spectrophotometer at 510nm wavelength in a 10mm cuvette.

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Calculation Amount of Fe in cooling water (in ppb) = 250 X absorbance X 1000 (mL sample) Example:Absorbance of PTP filter water sample on 26/06/2013 = 0.038 .. Amount of Fe = 250 X .038 = 190 ppb 50

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11.Test for determination of Zinc content in water from cooling tower:Reagents

DM water for make-up Sodium borate Zincon reagent

Procedure 1. A sample of 5 mL was taken in a 50mL volumetric flask. 2. Add 5mL of Sodium borate and 1.5mL Zincon reagent and let the solution stand for 5 minutes. 3. Make-up the volume to 50mL by adding DM water. 4. The sample was then analysed in spectrophotometer at 535nm wavelength in a 10mm cuvette. Calculation .. Amount of Zn (in ppm) = 0.056 X absorbance X 1000 (mL sample)

Fig. Zincon reagent.

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12.Test for determination of NH4+(as N) content in water from cooling tower :(I) Reagents

By Nesslers Reagent:-

DM water for make-up Nesslers Reagent Sodium-Potassium tartrate

Procedure 1. A sample of 5 mL was taken in a 50mL volumetric flask. 2. Add 5mL of Sodium-Potassium tartrate and 1mL Nesslers reagent and let the solution stand for 5 minutes. 3. Make-up the volume to 50mL by adding DM water. 4. The sample was then analysed in spectrophotometer at 410nm wavelength in a 10mm cuvette. Calculation Amount of NH4+ (in ppm) = 0.2986 X absorbance (mL sample) (II) Reagents

By Formaline:-

N/50 NaOH solution N/2 HCl solution Phenolphthalein indicator Formaline solution.

Procedure 1. A sample of 25 mL or 10mL (depending on the source of water) was taken in a 250mL conical flask. 2. Add 3 drops of phenolphthalein indicator to get a pink colour. 3. Add few drops of N/2 HCl so as to make the pink colour disappear. 4. Now add few drops of NaOH so that pink colour reappears. This is done to remove any excess alkalinity by hydroxides. 5. Add 15mL Formaline solution to the sample.
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If the Pink colour stays: Non-Traceable amount of NH4+as N is present. If the pink colour disappears: Titrate with N/50 NaOH to get an end-point of pink colour and note down the burette reading. Calculation:Amount of NH4+ (as N) = 11.2 X burette reading Example:Burette reading in Pond A sample on 26/06/13 = 14.2 mL .. Amount of NH4+(as N) = 11.2 X 14.2 = 159.04 mg/L

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13.Test for determination of Chloride content in water from cooling tower :Reagents

Potassium chromate indicator N/35.5 AgNO3

Procedure 1. A sample of 25 mL was taken in a 125mL erlenmeyer flask. 2. Three drops of Potassium chromate indicator was added to give a yellow colour to the sample. 3. The sample was titrated with N/35.5 AgNO3solution till the first slight brownish-red colour is observed. Calculation Amount of chloride (in mg/L) = 40 X (burette reading). Example:Burette reading in PTP FW sample on 03/07/2013 = 1.9 Amount of chloride = 40 X 1.9 = 76 mg/L

..

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14.Test for determination of Hydrazine(N2H4) content in feed-water from boiler :Here hydrazine is tested in feed-water from the boiler where it is added to remove dissolved oxygen which may cause corrosion inside the boiler. Reagents

DM water for make-up PDAB reagent. 1:9 Hydrochloric acid solution.

Procedure 1. A sample of 10 mL was taken from the boiler feed-water in a 50mL volumetric flask. 2. Add5 mL of1:9 HCl solution to the flask. 3. Add 5mL of PDAB solution and let the solution stand for 10 minutes. 4. Make-up the volume to 50mL by adding DM water. 5. The sample was then analysed in spectrophotometer at 460nm wavelength in a 10mm cuvette. Calculation Amount of N2H4(in ppm) = 34.7 X absorbance (mL sample) Example:- The observed absorbance was found to be 0.3458. Hence, amount of N2H4 = 34.7 X 0.3458 10 = 1.2 ppm in feed-water.

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15. Test for the determination of Chemical Oxygen Demand (C.O.D):In environmental chemistry, the chemical oxygen demand (COD) test is commonly used to indirectly measure the amount of organic compounds in water. Most applications of COD determine the amount of organic pollutants found in surface water (e.g. lakes and rivers) or wastewater, making COD a useful measure of water quality. It is expressed in milligrams per liter (mg/L), which indicates the mass of oxygen consumed per liter of solution. Procedure: 1. 2. 3. 4. Place 0.4gm of HgSO4in a reflux flask. Add 20mL sample of waste water. Add 10mL Potassium dichromate solution (N/10). Slowly add 30mL conc. H2SO4 (98%) and mix well. If the colour aliquot turns green, reduce the sample size or increase quantity of std. K2Cr2O7. 5. Add 0.3gm Ag2SO4 (If sample size changes, take fresh sample and follow all the above steps) 6. Connect the flask to condenser and mix well all the contents before heating. 7. Add glass beads to avoid bubbling before mixing. 8. Reflux for minimum 2 hours at 120 degree Celsius in COD apparatus. 9. Cool and then wash down the condenser with distilled water. 10.Dilute the aliquot to minimum of 150mL, cool and titrate excess K2Cr2O7 with N/10 FAS std. using Ferrian indicator. Sharp colour change from blue to wine-red at the end-point. Reflux blank in the same manner using DM water instead of sample. Calculation:COD (mg/L) = (A-B) X N X 8000 (mL sample) Where, A= mL of FAS for blank B= mL of FAS for sample N= Normality of FAS.
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Example:In Sewage Treatment Plant water sample, A= 8.0 mL ; B= 6.5mL ; sample volume= 20.0 mL .. COD = 60 mg/L In NFL backwater sample, A= 11.0 mL ; B= 10.5 mL ; .. COD = 10 mg/L

sample volume= 40.0 mL

COD std. preparation (APHA):1. Take Potassium Hydrogen Pthalate (KHP) std. 2. Lightly crush and then dry KHP to constant weight at 120 degrees Celsius. 3. Dissolve 425mg in distilled water and then dilute the aliquot to 1000mL. KHP has a theoretical COD of 500g O2/mL. This solution is stable when refrigerated for upto 3 months in the absence of biological growth. 4. Take 10mL above std. and 20mL of N/10 K2Cr2O7.

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16. Test for the determination of Bio-chemical Oxygen Demand (B.O.D) and Oxygen Saturation (DO):Biochemical oxygen demand or B.O.D. is the amount of dissolved oxygen needed by aerobic biological organisms in a body of water to break down organic material present in a given water sample at certain temperature over a specific time period. The term also refers to a chemical procedure for determining this amount. This is not a precise quantitative test, although it is widely used as an indication of the organic quality of water. [1] The BOD value is most commonly expressed in milligrams of oxygen consumed per litre of sample during 5 days of incubation at 20 C and is often used as a robust surrogate of the degree of organic pollution of water. BOD can be used as a gauge of the effectiveness of wastewater treatment plants. Oxygen saturation or dissolved oxygen (DO) is a relative measure of the amount of oxygen that is dissolved or carried in a given medium. It can be measured with a dissolved oxygen probe such as an oxygen sensor or an optode in liquid media, usually water. It has particular significance in medicine and environmental science.

Procedure: 1. Take sterilized 4 no. BOD bottle. 2. Add suitable amount of sample. 3. Add saturated oxygen DM water (SOD). Fill nutrient solution upto full BOD bottleneck, stopper BOD bottle and invert for mixing. 4. For estimation of 0th day value Add 2mL of MnSO4 reagent. Add 2mL of alkali iodide azide reagent. Add 5ml of conc. H2SO4. Stopper invert and mix well. Take 100mL sample and titrate with N/10 Na2S2O3 using starch as indicator. Run blank without sample following the same procedure. Remaining two bottle of sample and blank are kept in BOD incubator for 5 days at 20 degree Celsius.
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5. For estimation of 5th day value Add 2ml MnSO4. Add 2mL alkali azide solution. Add 5ml conc. H2SO4 Stopper, invert and mix. Estimate BOD by taking 100mL sample and titrating with N/80 Na2S2O3 using starch as indicator. Preparation of Reagent buffer solution: Dissolve 8.5g of KH2PO4, 21.75g of K2HPO4, 33.4g of Na2HPO4.7H2O and 1.7g of NH4Cl in 500mL of distilled water and dilute to 1liter thereafter. The pH should be 7.2 without further adjustment. BOD/DO calculation:DO (in mg/L) = 8 X volume of thio X F X 106 = 80 X sample volume X 1000 Calculation of BOD: Let, D0 = D.O. in sample bottle on 0th day D1 = D.O. in sample bottle on 5th day C0 = D.O. in blank bottle on 0th day C1 = D.O. in blank bottle on 5th day (C0-C1) = D.O. depletion in dilution water (D0-D1) = D.O. depletion in sample water BOD (mg/L) = {(D0 - D1) - (C0 - C1)} X F Where, F= dilution factor. 100 X R____ sample volume

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Preparation of BOD std. solution (IS-2488) Weigh 300mg/L of either glucose or sucrose or glutamic acid in the dilution flask. Std. glucose solution should show a BOD of 224 10 mg/L Std. glutamic acid should show a BOD of 217 10 mg/L. Take 100mL of the above solution and dilute to 1000mL. BOD value of glucose should come down to 22.4 10 mg/L and glutamic acid should show a BOD of 21.7 10 mg/L.

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EFFLUENT TREATMENT FACILITIES

M/s National Fertilizers Ltd. Has an Effluent Treatment Plant to cater to the waste-water generation from different sections of the plant. The schemes are based on maximum use of waste water and minimum discharge. Apart from the full scale treatment facilities several in plant pollution control measures have also been provided. An amount of Rs. 26.53 Crores approx. has been spent on Pollution Control Measures in two phases since commissioning of the plant. Cost of Pollution Control measures are given separately attached in the last page of the Annexure. The integrated effluent treatment facilities at NFL comprises of the following sections:I. Treatment of non ammonical effluent from cooling tower blow down, neutralized waste from ammonia plant and Acid & Alkali waste from Demineralized water plant. Removal of ammonia from Urea plant floor washing. Re-cycle and Treated Effluent ponds. Sewage Treatment plant.

II. III. IV.

I.

Treatment of Non-Ammonical Effluent

The Effluent Treatment plant has been designated for treatment 300 M3/hr. Cooling tower blow down along with 420 M3/day neutralized waste water from Ammonia plant and 35 M3/hr acidic waste anti 25 M3/hr alkaline waste from dematerialized water plant. Line diagram of plant is given at fig.1. The cooling tower blow-down effluents are received in a stilling chamber. All parameters of blow down effluents remain well within the limits as stipulated in MINAS. Hence this requires no specific treatment. The neutralized waste water from Ammonia plant is received either in the neutralized waste water collection tank or in the stilling chamber. The acidic waste and alkaline waste from DM plant are also received in the stilling chamber. The effluent then
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flows to reaction chambers. The 10% lime solution is used for maintaining the pH as and when required. No other chemicals except lime are used for pH correction of effluent water. The Treated effluent meeting MINAS is sent to Treated Effluent Pond from where it is pumped to horticulture water network for use in kitchen gardening in township.

II.

Treatment of Ammonical Effluent

The floor washings from Urea plant are collected in a storage tank from where it is pumped to pressure sand filters working in parallel for turbidity removal. The filtered ammoniac effluent is then taken to heat exchanger in which it is heated to 60 C with the help of Treated Effluent coming out of the steam stripper. The heated effluent is then taken to steam stripper for the removal of ammonia. The steam stripper is a hollow cylindrical vessel filled with packing materials. The effluent enters at the top and breaks into small droplets while passing through packing materials (rings). Low pressure steam enters at the bottom and rises up. The rising steam comes in contact with falling effluents. The ammonia being more volatile goes out of the stripper along with steam from top. The treated effluent, leaving the bottom of the stripper, meets parameters prescribed in MINAS. The treated effluent is sent to treat effluent pond. The line diagram for ammonia removal unit is given at fig.II.

III.

Treated Effluent and Recycle pond:-

Adequate provision is made for proper storage of recycle effluent and treated effluents before discharge as follows:a) A recycle pond with a capacity of 110000 M3 made of concrete with polythene and bitumen lining is provided to store any off grade effluent containing ammonia. The stored off grade effluent is recycled to effluent treatment plant for treatment of ammonia in air stripper and steam stripper before discharge. A treated effluent pond of capacity 220000 M3 which is made of concrete with polythene and bitumen lining is provided for storing the
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b)

treated effluent conforming to MINAS. The treated effluent is extensively used for horticulture in the factory premises and precincts.

IV.

Sewage Treatment Plant

The raw sewage consists mainly of spent water from kitchens, bathrooms, lavatories etc. Sewage contains only 0.1% solids, rest being water.

The Sewage Treatment Plant consists of Biological Treatment for removal of organic matter from the incoming sewage. Extended aeration process has been adopted for Sewage Treatment. Sewage from Township is collected in effluent collection pit through screen chamber. Collected sewage is pumped to the grit chamber through the help of Sewage transfer pumps. The sewage then flows into the aeration tank for aeration. The aeration tank is provided with mechanical fixed type surface aerator to supply oxygen to bacteria and to keep the biomass in suspension. The aerated mixed liquor is taken to clarifier by gravity whereas organic sludge is settled out at bottom while clear treated sewage is taken to chlorine contact chamber. The chlorine is dozed in the contact chamber by chlorinator. The chlorinated water is taken to the Treated Effluent pit from where it is pumped to horticulture water header for use in Van-Vihar for irrigation.

Part of the settled organic sludge is re-circulated back to aeration tank as seeding as the process is based on activated sludge process. The rest is bled-off into the sludge drying beds. The percolated water from sludge drying beds is collected into filtrate chamber from where it is taken to the effluent collection pit. The dried sludge is used as manure for horticulture purposes.

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OVERVIEW OF EFFLUENT TRESTMENT FACILITIES AT NFL The main plants i.e. Ammonia and Urea are designed for complete recycle of process and steam condensate to reduce the load on effluents. The important effluent facilities are summarized below:1) A highly efficient deep hydrolysis section has been installed in Urea Plant separately to treat the process condensate generated during urea production process. The Ammonia of the condensate is recovered and recycled back to the process. Finally treated water is of such a good quality that it is used in cooling tower as make up water or polished to produce Dematerialized water. In Ammonia Plant process condensate is treated by stripping with the help of steam and the recovered condensate is reused as boiler feed water after further treatment in Condensate Polishing Unit. The ammonical water is recycled back to the process. Oily waste water from the compressor houses of Ammonia and Urea Plants is skimmed off by DISC oil separator. Oil free water is discharged into treated effluent pond and the oil is recovered. The storm water drains going out from the complex have been blocked and the water is stored in specially made Guard Ponds. The collected water is used for horticulture purposes or treated in Effluent Treatment Plant depending upon its quality. These guard ponds work as 2nd line of defence and have been of considerable help in regulating effluent discharge. A highly sophisticated and efficient Effluent Treatment Plant has been installed to treat cooling tower blow down, neutralized waste from DM plant and ammonical wastes from various sections of the plants. The treated water always meets the specification as laid down by statutory authorities. Adequate provisions have been made to store both the contaminated as well as treated effluents. The contaminated (untreated) effluent (as & when it is generated during plant start-ups, shut down and upset
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2)

3)

4)

5)

6)

condition of plant) is stored in a corrosion resistant lined pond having a storage capacity of 0.11 million cubic metre. This water after treatment in Effluent. Treatment Plant is sent to the treated water pond for use in horticultural purposes. Treated Effluent Pond is also provided with anti-corrosive lining to prevent seepage and has a capacity to store 0.22 million cubic metre. This treated water is used for horticultural purposes in the factory, township and adjoining areas. 7) Township sewage is treated in a modern sewage treatment plant based on activated sludge process and the treated water is again being utilized for horticultural purposes. The solid waste generated is utilized as manure in green belt development.

Fig. SEWAGE TREATMENT PLANT AT N.F.L, VIJAIPUR

DOMESTIC SEWAGE

SUMP & PUMP

& CLARIFIER

CHLORI NATIO N

FINAL EFFLUENT

BAR SCREEN

PARTIAL FLUME
SLUDGE DRYING BEDS

TREATED EFFLUENT

FILTRATION

USED FOR HORTICULTURE PURPOSE

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CONCLUSION
The major raw material of NFL, Vijaipur is Natural gas which it obtains via HVJ pipeline and air from the surrounding which it utilizes to produce its chief commercial product UREA, which is about 3030 MT per day in Line-I and 3231 MT per day in Line-II.

By means of this vocational training I got an opportunity to learn, The various aspects of a large scale ammonia and urea production in a fertilizer plant like NFL. The importance of fertilizers in agriculture and their significant biological implications like Nitrogen fixation in plants. The chemistry of water plays an important role in any chemical industry be it fertilizers industry like NFL, or any other. I also got to learn about the chemistry, varied uses and quality testing and analysis methods of water. The various analytical instruments that are a necessity for any stringent scientific and methodical laboratory involved in Process analysis and quality assurance.

I hope that the information which I gained from all my mentors in the training shall be very helpful for me in my curriculum and my future endeavors.

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